Quantum Physics (UCSD Physics 130
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Feb. 6, 2008
2
Contents
0 Course Summary 0.1 Problems with Classical Physics . . . . . . . . . . . . . . . . . . . . . . . . 0.2 Thought Experiments on Diﬀraction . . . . . . . . . . . . . . . . . . . . . 0.3 Probability Amplitudes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.4 Wave Packets and Uncertainty . . . . . . . . . . . . . . . . . . . . . . . . 0.5 Operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.6 Expectation Values . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.7 Commutators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.8 The Schr¨dinger Equation . . . . . . . . . . . . . . . . . . . . . . . . . . o 0.9 Eigenfunctions, Eigenvalues and Vector Spaces . . . . . . . . . . . . . . . 0.10 A Particle in a Box . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.11 Piecewise Constant Potentials in One Dimension . . . . . . . . . . . . . . 0.12 The Harmonic Oscillator in One Dimension . . . . . . . . . . . . . . . . . 0.13 Delta Function Potentials in One Dimension . . . . . . . . . . . . . . . . 0.14 Harmonic Oscillator Solution with Operators . . . . . . . . . . . . . . . . 0.15 More Fun with Operators . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.16 Two Particles in 3 Dimensions . . . . . . . . . . . . . . . . . . . . . . . . 0.17 Identical Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.18 Some 3D Problems Separable in Cartesian Coordinates . . . . . . . . . . 0.19 Angular Momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.20 Solutions to the Radial Equation for Constant Potentials . . . . . . . . . 0.21 Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.22 Solution of the 3D HO Problem in Spherical Coordinates . . . . . . . . . 0.23 Matrix Representation of Operators and States . . . . . . . . . . . . . . . 0.24 A Study of = 1 Operators and Eigenfunctions . . . . . . . . . . . . . . . 0.25 Spin 1/2 and other 2 State Systems . . . . . . . . . . . . . . . . . . . . . 0.26 Quantum Mechanics in an Electromagnetic Field . . . . . . . . . . . . . . 0.27 Local Phase Symmetry in Quantum Mechanics and the Gauge Symmetry 0.28 Addition of Angular Momentum . . . . . . . . . . . . . . . . . . . . . . . 0.29 Time Independent Perturbation Theory . . . . . . . . . . . . . . . . . . . 0.30 The Fine Structure of Hydrogen . . . . . . . . . . . . . . . . . . . . . . . 0.31 Hyperﬁne Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.32 The Helium Atom . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.33 Atomic Physics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.34 Molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.35 Time Dependent Perturbation Theory . . . . . . . . . . . . . . . . . . . . 0.36 Radiation in Atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.37 Classical Field Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.38 The Classical Electromagnetic Field . . . . . . . . . . . . . . . . . . . . . 0.39 Quantization of the EM Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 18 18 18 19 20 20 21 21 21 23 23 25 25 26 27 28 29 29 29 31 31 32 32 33 34 34 35 37 38 39 40 41 42 43 44 44 47 47 49
3 0.40 0.41 0.42 0.43 1 The 1.1 1.2 1.3 1.4 1.5 Scattering of Photons Electron Self Energy . The Dirac Equation . The Dirac Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51 52 53 60 64 65 70 72 74 76 78 78 78 79 79 80 80 82 83 84 84 87 87 90 91 92 96 96 96 97 98 99 99 99 100
1.6
1.7
Problems with Classical Physics Black Body Radiation * . . . . . . . . . . . . . . . . . . . . . . . The Photoelectric Eﬀect . . . . . . . . . . . . . . . . . . . . . . . The Rutherford Atom * . . . . . . . . . . . . . . . . . . . . . . . Atomic Spectra * . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.4.1 The Bohr Atom * . . . . . . . . . . . . . . . . . . . . . . Derivations and Computations . . . . . . . . . . . . . . . . . . . 1.5.1 Black Body Radiation Formulas * . . . . . . . . . . . . . 1.5.2 The Fine Structure Constant and the Coulomb Potential Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.6.1 The Solar Temperature * . . . . . . . . . . . . . . . . . . 1.6.2 Black Body Radiation from the Early Universe * . . . . . 1.6.3 Compton Scattering * . . . . . . . . . . . . . . . . . . . . 1.6.4 Rutherford’s Nuclear Size * . . . . . . . . . . . . . . . . . Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . .
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2 Diﬀraction 2.1 Diﬀraction from Two Slits . . . . . . . . . . . . . . . . . . 2.2 Single Slit Diﬀraction . . . . . . . . . . . . . . . . . . . . 2.3 Diﬀraction from Crystals . . . . . . . . . . . . . . . . . . 2.4 The DeBroglie Wavelength . . . . . . . . . . . . . . . . . 2.4.1 Computing DeBroglie Wavelengths . . . . . . . . . 2.5 Wave Particle Duality (Thought Experiments) . . . . . . 2.6 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6.1 Intensity Distribution for Two Slit Diﬀraction * . 2.6.2 Intensity Distribution for Single Slit Diﬀraction * . 2.7 Sample Test Problems . . . . . . . . . . . . . . . . . . . . 3 The Solution: Probability Amplitudes 3.1 Derivations and Computations . . . . 3.1.1 Review of Complex Numbers . 3.1.2 Review of Traveling Waves . . 3.2 Sample Test Problems . . . . . . . . .
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4 Wave Packets 101 4.1 Building a Localized SingleParticle Wave Packet . . . . . . . . . . . . . . . . . . . . 101 4.2 Two Examples of Localized Wave Packets . . . . . . . . . . . . . . . . . . . . . . . . 102 4.3 The Heisenberg Uncertainty Principle . . . . . . . . . . . . . . . . . . . . . . . . . . 103
4 4.4 4.5 4.6 Position Space and Momentum Space . . . . . . . . . . . . . . . . . . . . . . . . . . 104 Time Development of a Gaussian Wave Packet * . . . . . . . . . . . . . . . . . . . . 105 Derivations and Computations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106 4.6.1 4.6.2 4.6.3 4.6.4 4.6.5 4.6.6 4.6.7 4.7 4.7.1 4.7.2 4.7.3 4.7.4 4.7.5 4.7.6 4.8 Fourier Series * . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106 Fourier Transform * . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107 Integral of Gaussian . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107 Fourier Transform of Gaussian * . . . . . . . . . . . . . . . . . . . . . . . . . 108 Time Dependence of a Gaussian Wave Packet * . . . . . . . . . . . . . . . . . 110 Numbers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 The Dirac Delta Function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112 The Square Wave Packet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112 The Gaussian Wave Packet * . . . . . . . . . . . . . . . . . . . . . . . . . . . 113 The Dirac Delta Function Wave Packet * . . . . . . . . . . . . . . . . . . . . 113 Can I “See” inside an Atom . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113 Can I “See” inside a Nucleus . . . . . . . . . . . . . . . . . . . . . . . . . . . 114 Estimate the Hydrogen Ground State Energy . . . . . . . . . . . . . . . . . . 114
Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115 118 The Momentum Operator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118 The Energy Operator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119 The Position Operator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119 The Hamiltonian Operator . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
5 Operators 5.1 5.1.1 5.1.2 5.1.3 5.1.4 5.2 5.3 5.4 5.5 5.6
Operators in Position Space . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
Operators in Momentum Space . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119 Expectation Values . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120 Dirac Braket Notation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121 Commutators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121 Derivations and Computations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122 5.6.1 5.6.2 Verify Momentum Operator . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122 Verify Energy Operator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123 Expectation Value of Momentum in a Given State . . . . . . . . . . . . . . . 123 Commutator of E and t . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124 Commutator of E and x . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124 Commutator of p and xn Commutator of Lx and Ly . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
5.7
Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123 5.7.1 5.7.2 5.7.3 5.7.4 5.7.5
5.8
Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
5 6 The Schr¨dinger Equation o 6.1 6.2 6.3 6.4 6.5 127
Deriving the Equation from Operators . . . . . . . . . . . . . . . . . . . . . . . . . . 127 The Flux of Probability * . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128 The Schr¨dinger Wave Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129 o The Time Independent Schr¨dinger Equation . . . . . . . . . . . . . . . . . . . . . . 129 o Derivations and Computations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130 6.5.1 6.5.2 Linear Operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130 Probability Conservation Equation * . . . . . . . . . . . . . . . . . . . . . . . 131 Solution to the Schr¨dinger Equation in a Constant Potential . . . . . . . . . 131 o
6.6 6.7
Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131 6.6.1 Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132 133
7 Eigenfunctions, Eigenvalues and Vector Spaces 7.1 7.2 7.3 7.4 7.5 7.6 7.7
Eigenvalue Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133 Hermitian Conjugate of an Operator . . . . . . . . . . . . . . . . . . . . . . . . . . . 134 Hermitian Operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135 Eigenfunctions and Vector Space . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136 The Particle in a 1D Box . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137 7.5.1 The Same Problem with Parity Symmetry . . . . . . . . . . . . . . . . . . . . 139 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140 Momentum Eigenfunctions 7.7.1 7.7.2
Derivations and Computations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141 Eigenfunctions of Hermitian Operators are Orthogonal . . . . . . . . . . . . . 141 Continuity of Wavefunctions and Derivatives . . . . . . . . . . . . . . . . . . 142 Hermitian Conjugate of a Constant Operator . . . . . . . . . . . . . . . . . . 143 Hermitian Conjugate of
∂ ∂x
7.8
Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143 7.8.1 7.8.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
7.9
Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143 146
8 One Dimensional Potentials 8.1 8.1.1 8.1.2 8.1.3 8.1.4 8.1.5 8.2 8.3 8.4 8.5 8.6 8.7
Piecewise Constant Potentials in 1D . . . . . . . . . . . . . . . . . . . . . . . . . . . 146 The General Solution for a Constant Potential . . . . . . . . . . . . . . . . . 146 The Potential Step . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146 The Potential Well with E > 0 * . . . . . . . . . . . . . . . . . . . . . . . . . 148 Bound States in a Potential Well * . . . . . . . . . . . . . . . . . . . . . . . . 150 The Potential Barrier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
The 1D Harmonic Oscillator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154 The Delta Function Potential * . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156 The Delta Function Model of a Molecule * . . . . . . . . . . . . . . . . . . . . . . . . 157 The Delta Function Model of a Crystal * . . . . . . . . . . . . . . . . . . . . . . . . 159 The Quantum Rotor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161 Derivations and Computations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161 8.7.1 Probability Flux for the Potential Step * . . . . . . . . . . . . . . . . . . . . 161
6 8.7.2 Scattering from a 1D Potential Well * . 8.7.3 Bound States of a 1D Potential Well * . 8.7.4 Solving the HO Diﬀerential Equation * 8.7.5 1D Model of a Molecule Derivation * . . 8.7.6 1D Model of a Crystal Derivation * . . Examples . . . . . . . . . . . . . . . . . . . . . Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162 164 165 168 169 171 171 174 175 176 176 178 178 179 179 179 179 180
8.8 8.9
9 Harmonic Oscillator Solution using Operators 9.1 Introducing A and A† . . . . . . . . . . . . . . . . . . . . . 9.2 Commutators of A, A† and H . . . . . . . . . . . . . . . . . 9.3 Use Commutators to Derive HO Energies . . . . . . . . . . 9.3.1 Raising and Lowering Constants . . . . . . . . . . . 9.4 Expectation Values of p and x . . . . . . . . . . . . . . . . . 9.5 The Wavefunction for the HO Ground State . . . . . . . . . 9.6 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9.6.1 The expectation value of x in eigenstate . . . . . . . 9.6.2 The expectation value of p in eigenstate . . . . . . . 1 9.6.3 The expectation value of x in the state √2 (u0 + u1 ). 9.6.4
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The expectation value of 1 mω 2 x2 in eigenstate . . . . . . . . . . . . . . . . . 180 2
9.7
p 9.6.5 The expectation value of 2m in eigenstate . . . . . . . . . . . . . . . . . . . . 181 9.6.6 Time Development Example . . . . . . . . . . . . . . . . . . . . . . . . . . . 181 Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
10 More Fun with Operators 10.1 Operators in a Vector Space . . . . . . . . . . . . . . 10.1.1 Review of Operators . . . . . . . . . . . . . . 10.1.2 Projection Operators j j and Completeness 10.1.3 Unitary Operators . . . . . . . . . . . . . . . 10.2 A Complete Set of Mutually Commuting Operators . 10.3 Uncertainty Principle for NonCommuting Operators 10.4 Time Derivative of Expectation Values * . . . . . . . 10.5 The Time Development Operator * . . . . . . . . . . 10.6 The Heisenberg Picture * . . . . . . . . . . . . . . . 10.7 Examples . . . . . . . . . . . . . . . . . . . . . . . . 10.7.1 Time Development Example . . . . . . . . . 10.8 Sample Test Problems . . . . . . . . . . . . . . . . . 11 Extending QM to Two Particles and Three 11.1 Quantum Mechanics for Two Particles . . . 11.2 Quantum Mechanics in Three Dimensions . 11.3 Two Particles in Three Dimensions . . . . . 11.4 Identical Particles . . . . . . . . . . . . . . 11.5 Sample Test Problems . . . . . . . . . . . .
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184 184 184 185 186 186 187 188 189 190 191 191 191 193 193 194 194 196 196
Dimensions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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7 12 3D Problems Separable in Cartesian Coordinates 198
12.1 Particle in a 3D Box . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198 12.1.1 Filling the Box with Fermions . . . . . . . . . . . . . . . . . . . . . . . . . . . 199 12.1.2 Degeneracy Pressure in Stars . . . . . . . . . . . . . . . . . . . . . . . . . . . 200 12.2 The 3D Harmonic Oscillator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202 12.3 Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203 13 Angular Momentum 204
13.1 Rotational Symmetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204 13.2 Angular Momentum Algebra: Raising and Lowering Operators . . . . . . . . . . . . 206 13.3 The Angular Momentum Eigenfunctions . . . . . . . . . . . . . . . . . . . . . . . . . 207 13.3.1 Parity of the Spherical Harmonics . . . . . . . . . . . . . . . . . . . . . . . . 210 13.4 Derivations and Computations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210 13.4.1 Rotational Symmetry Implies Angular Momentum Conservation . . . . . . . 210 13.4.2 The Commutators of the Angular Momentum Operators . . . . . . . . . . . . 211 13.4.3 Rewriting
p2 2μ
Using L2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
13.4.4 Spherical Coordinates and the Angular Momentum Operators . . . . . . . . . 213 13.4.5 The Operators L± . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216 13.5 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217 13.5.1 The Expectation Value of Lz . . . . . . . . . . . . . . . . . . . . . . . . . . . 217 13.5.2 The Expectation Value of Lx . . . . . . . . . . . . . . . . . . . . . . . . . . . 218 13.6 Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218 14 The Radial Equation and Constant Potentials * 220
14.1 The Radial Equation * . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220 14.2 Behavior at the Origin * . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220 14.3 Spherical Bessel Functions * . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221 14.4 Particle in a Sphere * . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223 14.5 Bound States in a Spherical Potential Well * . . . . . . . . . . . . . . . . . . . . . . 223 14.6 Partial Wave Analysis of Scattering * . . . . . . . . . . . . . . . . . . . . . . . . . . 225 14.7 Scattering from a Spherical Well * . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226 14.8 The Radial Equation for u(r) = rR(r) * . . . . . . . . . . . . . . . . . . . . . . . . . 228 14.9 Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229 15 Hydrogen 230
15.1 The Radial Wavefunction Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231 15.2 The Hydrogen Spectrum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235 15.3 Derivations and Calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236 15.3.1 Solution of Hydrogen Radial Equation * . . . . . . . . . . . . . . . . . . . . . 236 15.3.2 Computing the Radial Wavefunctions * . . . . . . . . . . . . . . . . . . . . . 238 15.4 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240 15.4.1 Expectation Values in Hydrogen States . . . . . . . . . . . . . . . . . . . . . 240
8 15.4.2 The Expectation of
1 r
in the Ground State . . . . . . . . . . . . . . . . . . . . 241
15.4.3 The Expectation Value of r in the Ground State . . . . . . . . . . . . . . . . 241 15.4.4 The Expectation Value of vr in the Ground State . . . . . . . . . . . . . . . . 241 15.5 Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242 16 3D Symmetric HO in Spherical Coordinates * 17 Operators Matrices and Spin 245 249
17.1 The Matrix Representation of Operators and Wavefunctions . . . . . . . . . . . . . . 249 17.2 The Angular Momentum Matrices* . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250 17.3 Eigenvalue Problems with Matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251 17.4 An = 1 System in a Magnetic Field* . . . . . . . . . . . . . . . . . . . . . . . . . . 253 17.5 Splitting the Eigenstates with SternGerlach . . . . . . . . . . . . . . . . . . . . . . . 253 17.6 Rotation operators for = 1 * . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256 17.7 A Rotated SternGerlach Apparatus* . . . . . . . . . . . . . . . . . . . . . . . . . . 257 17.8 Spin 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257 2 17.9 Other Two State Systems* . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261 17.9.1 The Ammonia Molecule (Maser) . . . . . . . . . . . . . . . . . . . . . . . . . 261 17.9.2 The Neutral Kaon System* . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262 17.10Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262 17.10.1 Harmonic Oscillator Hamiltonian Matrix . . . . . . . . . . . . . . . . . . . . 262 17.10.2 Harmonic Oscillator Raising Operator . . . . . . . . . . . . . . . . . . . . . . 262 17.10.3 Harmonic Oscillator Lowering Operator . . . . . . . . . . . . . . . . . . . . . 263 17.10.4 Eigenvectors of Lx . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263 17.10.5 A 90 degree rotation about the z axis. . . . . . . . . . . . . . . . . . . . . . . 264 17.10.6 Energy Eigenstates of an = 1 System in a Bﬁeld . . . . . . . . . . . . . . . 265 17.10.7 A series of SternGerlachs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266 17.10.8 Time Development of an = 1 System in a Bﬁeld: Version I . . . . . . . . . 268 17.10.9 Expectation of Sx in General Spin 17.10.10 Eigenvectors of Sx for Spin 17.10.11 Eigenvectors of Sy for Spin
1 2 1 2 1 2 1 2
State . . . . . . . . . . . . . . . . . . . . 269
. . . . . . . . . . . . . . . . . . . . . . . . . . . 269 . . . . . . . . . . . . . . . . . . . . . . . . . . . 271 State in a B ﬁeld . . . . . . . . . . . . . . . . 272
17.10.12 Eigenvectors of Su . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271 17.10.13 Time Development of a Spin 17.10.14 Nuclear Magnetic Resonance (NMR and MRI) . . . . . . . . . . . . . . . . . 273 17.11Derivations and Computations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275 17.11.1 The = 1 Angular Momentum Operators* . . . . . . . . . . . . . . . . . . . 275 17.11.2 Compute [Lx , Ly ] Using Matrices * . . . . . . . . . . . . . . . . . . . . . . . . 276 17.11.3 Derive the Expression for Rotation Operator Rz * . . . . . . . . . . . . . . . 276 17.11.4 Compute the = 1 Rotation Operator Rz (θz ) * . . . . . . . . . . . . . . . . . 277 17.11.5 Compute the = 1 Rotation Operator Ry (θy ) * . . . . . . . . . . . . . . . . 277 17.11.6 Derive Spin 1 Operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278 2 17.11.7 Derive Spin
1 2
Rotation Matrices * . . . . . . . . . . . . . . . . . . . . . . . . 279
9 17.11.8 NMR Transition Rate in a Oscillating B Field . . . . . . . . . . . . . . . . . . 280 17.12Homework Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281 17.13Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282 18 Homework Problems 130A 284
18.1 HOMEWORK 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284 18.2 Homework 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285 18.3 Homework 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286 18.4 Homework 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287 18.5 Homework 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288 18.6 Homework 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289 18.7 Homework 7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290 18.8 Homework 8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291 18.9 Homework 9 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292 19 Electrons in an Electromagnetic Field 293
19.1 Review of the Classical Equations of Electricity and Magnetism in CGS Units . . . . 293 19.2 The Quantum Hamiltonian Including a Bﬁeld . . . . . . . . . . . . . . . . . . . . . 294 19.3 Gauge Symmetry in Quantum Mechanics . . . . . . . . . . . . . . . . . . . . . . . . 296 19.4 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299 19.4.1 The Naive Zeeman Splitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299 19.4.2 A Plasma in a Magnetic Field . . . . . . . . . . . . . . . . . . . . . . . . . . . 299 19.5 Derivations and Computations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300 19.5.1 Deriving Maxwell’s Equations for the Potentials . . . . . . . . . . . . . . . . 300 19.5.2 The Lorentz Force from the Classical Hamiltonian . . . . . . . . . . . . . . . 302 19.5.3 The Hamiltonian in terms of B . . . . . . . . . . . . . . . . . . . . . . . . . . 304 19.5.4 The Size of the B ﬁeld Terms in Atoms . . . . . . . . . . . . . . . . . . . . . 305 19.5.5 Energy States of Electrons in a Plasma I . . . . . . . . . . . . . . . . . . . . . 305 19.5.6 Energy States of Electrons in a Plasma II . . . . . . . . . . . . . . . . . . . . 307 19.5.7 A Hamiltonian Invariant Under Wavefunction Phase (or Gauge) Transformations308 19.5.8 Magnetic Flux Quantization from Gauge Symmetry . . . . . . . . . . . . . . 309 19.6 Homework Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310 19.7 Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310 20 Addition of Angular Momentum 311
20.1 Adding the Spins of Two Electrons . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311 20.2 Total Angular Momentum and The Spin Orbit Interaction . . . . . . . . . . . . . . . 312 20.3 Adding Spin
1 2
to Integer Orbital Angular Momentum . . . . . . . . . . . . . . . . . 313
20.4 Spectroscopic Notation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313 20.5 General Addition of Angular Momentum: The ClebschGordan Series . . . . . . . . 314 20.6 Interchange Symmetry for States with Identical Particles . . . . . . . . . . . . . . . . 315 20.7 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
10 20.7.1 Counting states for 20.7.3 Adding = 4 to = 3 Plus spin
1 2
. . . . . . . . . . . . . . . . . . . . . . . 315
1 2
20.7.2 Counting states for Arbitrary
Plus spin
. . . . . . . . . . . . . . . . . . . 316
= 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 316
20.7.4 Two electrons in an atomic P state . . . . . . . . . . . . . . . . . . . . . . . . 317 20.7.5 The parity of the pion from πd → nn. . . . . . . . . . . . . . . . . . . . . . . 317 20.8 Derivations and Computations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318 20.8.1 Commutators of Total Spin Operators . . . . . . . . . . . . . . . . . . . . . . 318 20.8.2 Using the Lowering Operator to Find Total Spin States . . . . . . . . . . . . 318 20.8.3 Applying the S 2 Operator to χ1m and χ00 . . . . . . . . . . . . . . . . . . . . 319 20.8.4 Adding any plus spin 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320 2
1
20.8.5 Counting the States for 
−
2
≤j≤
1
+
2.
. . . . . . . . . . . . . . . . . 323
20.9 Homework Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323 20.10Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324 21 Time Independent Perturbation Theory 326
21.1 The Perturbation Series . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 326 21.2 Degenerate State Perturbation Theory . . . . . . . . . . . . . . . . . . . . . . . . . . 327 21.3 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328 21.3.1 H.O. with anharmonic perturbation (ax4 ). . . . . . . . . . . . . . . . . . . . . 328 21.3.2 Hydrogen Atom Ground State in a Eﬁeld, the Stark Eﬀect. . . . . . . . . . . 329 21.3.3 The Stark Eﬀect for n=2 Hydrogen. . . . . . . . . . . . . . . . . . . . . . . . 330 21.4 Derivations and Computations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332 21.4.1 Derivation of 1st and 2nd Order Perturbation Equations . . . . . . . . . . . . 332 21.4.2 Derivation of 1st Order Degenerate Perturbation Equations . . . . . . . . . . 333 21.5 Homework Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 334 21.6 Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335 22 Fine Structure in Hydrogen 336
22.1 Hydrogen Fine Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336 22.2 Hydrogen Atom in a Weak Magnetic Field . . . . . . . . . . . . . . . . . . . . . . . . 339 22.3 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341 22.4 Derivations and Computations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341 22.4.1 The Relativistic Correction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341 22.4.2 The SpinOrbit Correction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341 22.4.3 Perturbation Calculation for Relativistic Energy Shift . . . . . . . . . . . . . 342 22.4.4 Perturbation Calculation for H2 Energy Shift . . . . . . . . . . . . . . . . . . 343 22.4.5 The Darwin Term . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343 22.4.6 The Anomalous Zeeman Eﬀect . . . . . . . . . . . . . . . . . . . . . . . . . . 344 22.5 Homework Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345 22.6 Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
11 23 Hyperﬁne Structure 348
23.1 Hyperﬁne Splitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348 23.2 Hyperﬁne Splitting in a B Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349 23.3 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351 23.3.1 Splitting of the Hydrogen Ground State . . . . . . . . . . . . . . . . . . . . . 351 23.3.2 Hyperﬁne Splitting in a Weak B Field . . . . . . . . . . . . . . . . . . . . . . 352 23.3.3 Hydrogen in a Strong B Field . . . . . . . . . . . . . . . . . . . . . . . . . . . 353 23.3.4 Intermediate Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353 23.3.5 Positronium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354 23.3.6 Hyperﬁne and Zeeman for H, muonium, positronium . . . . . . . . . . . . . . 355 23.4 Derivations and Computations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356 23.4.1 Hyperﬁne Correction in Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . 356 23.5 Homework Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358 23.6 Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358 24 The Helium Atom 359
24.1 General Features of Helium States . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359 24.2 The Helium Ground State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361 24.3 The First Excited State(s) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361 24.4 The Variational Principle (RayleighRitz Approximation) . . . . . . . . . . . . . . . 364 24.5 Variational Helium Ground State Energy . . . . . . . . . . . . . . . . . . . . . . . . 365 24.6 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367 24.6.1 1D Harmonic Oscillator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367 24.6.2 1D H.O. with exponential wavefunction . . . . . . . . . . . . . . . . . . . . . 367 24.7 Derivations and Computations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 368 24.7.1 Calculation of the ground state energy shift . . . . . . . . . . . . . . . . . . . 368 24.8 Homework Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 370 24.9 Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 370 25 Atomic Physics 372
25.1 Atomic Shell Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 372 25.2 The Hartree Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 373 25.3 Hund’s Rules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 373 25.4 The Periodic Table . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 374 25.5 The Nuclear Shell Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377 25.6 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379 25.6.1 Boron Ground State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379 25.6.2 Carbon Ground State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379 25.6.3 Nitrogen Ground State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380 25.6.4 Oxygen Ground State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382 25.7 Homework Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382 25.8 Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382
. 390 26. . . . . . . . . . .1 The 2P to 1S Decay Rate in Hydrogen . 383
26. . . . . . . . . . . . . . . . . . . . . . . . . . .3 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7 Examples . . . . . . . . . . . . . . 410 28. . . . . . . . . . . . . . . . . . . . . . . .10Sample Test Problems . . . . . . . . . . . . . . . . . 411 28. . . . . . . . . . . . . . . . . . . . . 412 28. . . . . . . . . . . . . . . . . . . . . . . . . . . .1 The M¨ssbauer Eﬀect . .13Examples . . . . . . .4 Derivations and Computations . .7 General Unpolarized Initial State . . . . . . . . . .6 Explicit 2p to 1s Decay Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391 27. . . . . 390 26. . . . . . . . . . . . . . . . . . . . . 396 27. . . . . . . 416
. . . . . . . . . . . . .12Phenomena of Radiation Theory . . .6 Rotational States . .8 Angular Distributions . . . . . . . . . . . . . . . . . . .5 Electric Dipole Approximation and Selection Rules .5 Homework Problems . . . . . . . . . . . . . . . . . . . . . . . . . 409 28. . . . . . 401 28. . . . . . . . . . . . . . . . . . .4 Total Decay Rate Using Phase Space . . . . .6 Sample Test Problems . . . . . . .12 26 Molecular Physics 26. . . . . . . . . . . . . . . . . . . . .4. . . . . .13. . .12. . . . . . . . . . . .5 Vibrational States . . . . . . . .11Lifetime and Line Width . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402 28. . . . . . . 388 26. . . . . . . . . . 406 28. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 386 26. . . . . .2 Decay Rates for the Emission of Photons .9 Homework Problems . . . . . . . . . . . . 416 28. . . . . .3. . . 390 26. . . . . . . . . . . . . . 385 26. . . . . .1 Harmonic Oscillator in a Transient E Field . .2 The H2 Molecule .9 Vector Operators and the Wigner Eckart Theorem . 413 28. . . . 409 28. . . . . . . . . . . . . . . . . . . . . . .1 Energy in Field for a Given Vector Potential . . . . 393 27.1 The Delta Function of Energy Conservation . . .4 Molecular Orbitals . . . . . . . . . . . . .8 Derivations and Computations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389 26. . . . . 398 28. . . . . . . . . . .12. . . . . .2 LASERs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 400 28. . . . . . . .1 The H+ 2 383
Ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413 o 28. . . . . . . . .2 Sinusoidal Perturbations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405 28. . . . . . . 414 28. . . . .14Derivations and Computations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1 Other Phenomena Inﬂuencing Line Width . 396 27. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 416 28. . . . . . . . . . . . 395 27. . . . . . . . . . . . .3 Importance of Unpaired Valence Electrons . . .1 The Photon Field in the Quantum Hamiltonian . . . . . . . . . . . . . . . . . . . . . 416 28. . . . . . . . . . . . . . . .1 General Time Dependent Perturbations . . . . . . . . . . . . . . . . . . . . . 400 28. . . . . . . . . . . . 395 27. . . . . . . . . . . . . . . . . . . . . . . . 386 26. . . .14. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397 28 Radiation in Atoms 398
28. . . . . . . . . . .3 Phase Space: The Density of Final States . . . . . . .10Exponential Decay . . . . . . 397 27. . . . .11. . . . . . 390 27 Time Dependent Perturbation Theory 391
27. . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . 457 32. . . . . . . . . 417 28. . . . . . . . .4 Sample Test Problems . . . . . . . . . . . . . .2 Classical Scalar Field in Four Dimensions . . . . . . . . . . . . . . . .15Homework Problems . .13Black Body Radiation Spectrum . . . . . . . . . . . . . 455 32. .12. . . . . . . .6 Photon States . . . . . . . . 427 29. . . . . . . . 451 32. . . . . . . . . . . . . . . . .14. . . . . . . . . . . . . . . . . . . . . . . . 430 30. . . . . . . . . . . . . . . . . .3 Estimate of Atomic Decay Rate . . . . . . . . . . 454 32. . . . . . . . . . . . . .5 Quantization of the Oscillators . . . . . 417 28. . . . . . . . . . . . . . . . .5 Homework Problems . . . . . . 449 32. . . . . . . . . . . . . . . . . . .14Homework Problems . . . . . . . . . . 437 31 Classical Maxwell Fields 438
31. . . . . . . . . . . . . . 428 30. . . . . . . . . . . . .11Emission and Absorption of Photons by Atoms . . 426 29. . . . . . . . . . . . . . . . . . . . . . . . .14. . . . . . . . . 445 32. . . . . . . . . . . . . . 443 31. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1 Rationalized HeavisideLorentz Units . . . . . . . . . . . . . . 446 32. . . . . . . . . . .2 Scattering from a Hard Sphere . . . . . . 448 32. . . . . . . . . . . . . . . . 461 32. . . . . . . . . . . . . .1 Transverse and Longitudinal Fields . .7 Fermion Operators .16Sample Test Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . .13 28. . . . . . . . . . . . . . . . . . . .8 Quantized Radiation Field . 444 32 Quantum Theory of Radiation 445
32. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10Uncertainty Relations and RMS Field Fluctuations . . . . . . . . . . . . . . . . . . . . 441 31. . . . . . . . . . . . . .1 Simple Mechanical Systems and Fields . . . . . . . . . . . . . . . . . . . . . . . . .2 The Electromagnetic Field Tensor . . . . . . . . . . . . . . . . . . . . . 459 32. .3 Homework Problems . . . . . . . . . . . . . . . . .3 The Hamiltonian for the Radiation Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457 32. . . . 439 31. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3 The Lagrangian for Electromagnetic Fields . . . . .1 Beyond the Electric Dipole Approximation . . . . . . . . . . . . . . . . . . . . . . . 463 32. . . . . . . . . . . . . . . . . . . . . . . . . .4 Canonical Coordinates and Momenta . . . . . . . . . . . . . . . . 419 29 Scattering 421
29. . . . . . . . . . . . 425 29. 460 32. . . . . . . . . . . . . 464
. . . . . 438 31. . . . . .2 Fourier Decomposition of Radiation Oscillators . 454 32. . . . . . . . . . . . . . . .12Review of Radiation of Photons . . . . .3 Homework Problems . 427 30 Classical Scalar Fields 428
30. . . . . . . . . . . . . . . . . . . . . . . . . . .4 Gauge Invariance can Simplify Equations . . . . . . . 416 28. . . . . . . . . . . . . . . . . . . . . . . . . .9 The Time Development of Field Operators . . . . . . . . . . . . .2 General Phase Space Formula . . . . . .1 Scattering from a Screened Coulomb Potential . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12Constants of the Motion for a Free Particle . . . . . . . 472 33.1 Dirac Particle at Rest . . . . . . . . 546
. . . . . . . . . . . . . . . . . . . . . 536 35. . . . . . . . . . . . 539 35. . . . . . . .14. . . . . . . . . . . . . . . . . . . . . . . 524 35. . . . . . . . . . . . . . . . . . . . .6. . . . . . . . . . . . . .3 The Expected Velocity and Zitterbewegung . . . . . . . . 490 o 35. . . . . . . . . . . .3 The Dirac Equation . 489 35. . . . . . .14. . . . . . . . . . .3 Alternate Labeling of the Plane Wave Solutions . . . . . . . . . . . . . . . . . . . . . . .18Charge Conjugate Waves . . 500 35. . . 511 35. . .20The Quantized Dirac Field with Positron Spinors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526 35. . . . . .13The Relativistic Interaction Hamiltonian . . . . .1 Velocity Operator and Zitterbewegung . . . . . .4 Thomson Scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527 35. . . . . .2 The Large and Small Components of the Dirac Wavefunction . .16Thomson Scattering . . . . . .7 “Negative Energy” Solutions: Hole Theory . . . . . . . . . . .11Bilinear Covariants . . . . . . . . . 523 35. . . . . . . . . . . . . . . . . . .1 The Lamb Shift . . . .8 Equivalence of a Two Component Theory . . . . . . . . . . . . . . . .5. . . 503 35. . . . . . . . . . . . . . . .5 Raman Eﬀect . . . . . . . 501 35. . . . . 521 35. . . . . . . . . . . . . . . . . . . . . . . . . . . . 494 35. . . . . . . 475 33. . . . . . . . 543 35. . . . . . . . . . . . . . . . . . . . . . . .2 Elastic Scattering . . . . . .4 The Conserved Probability Current . . . . . . . . . . .17Hole Theory and Charge Conjugation . . . . . . .1 The Two Component Dirac Equation . 491 35. . . . . .14 33 Scattering of Photons 467
33. . . .2 Dirac Plane Wave Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 540 35. . . . . 524 35. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6. . . 526 35. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6 Homework Problems . . . . . . . . . . . . . . 473 33. . . . . . . . . . . . . . . . . . 510 35.1 Resonant Scattering . . . . . . . . 512 35. .3 Rayleigh Scattering . . . . . .1 Dirac’s Motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . .3 The NonRelativistic Equation . . . . .2 Homework Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . .15Solution of the Dirac Equation for Hydrogen . . . . . . . . . . . . . . . . 497 35. . . . . . . . . . . . . . . 476 33. . . . . . . . . . . . . . . . . . 496 35. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 476 34 Electron Self Energy Corrections 477
34. . . . . . . . . . . . . . . . . . . . . . 519 35. . .10Parity .5 The Nonrelativistic Limit of the Dirac Equation . . . . . . . . .14. . . . . . 484 34. . 497 35. . . . . . . . . . . . . . 474 33. . . . . . . . . . . . . . . . . . . . . . . . . . . . 496 35. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .14Phenomena of Dirac States . . . . . . . .9 Relativistic Covariance . . . . . . . . . . . . 518 35.6 Solution of Dirac Equation for a Free Particle . . . . 509 35.6. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5. . . . . . . . . . . . . . . . . . .5. . . . . . . . . . . .2 The Schr¨dingerPauli Hamiltonian . . . . . . . . . . . . . . . . . . . . . . . . . 488 35 Dirac Equation 489
35.19Quantization of the Dirac Field . . . . . . . . .2 Expansion of a State in Plane Waves .
. . . . . . . . . . . . . . . . .24Homework Problems . .15 35. . . . . . . . . . . . .22The QED LaGrangian and Gauge Invariance . . . . . . . . . . . . .21Vacuum Polarization . . . 550 35. . . . . . . . . . . . . . . . . . . . . . . . . . . 548 35. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 547 35. . . . . . . . . . . . . . 550 36 Formulas 551
.23Interaction with a Scalar Field . . . . . . . . .
• To make all the class material including a complete set of lecture notes available to students on the WorldWide Web. with less steps skipped than in standard textbooks. the html is generated from LaTeX input. Eventually.16
Preface
These notes represent an experiment in the use of information technology in teaching an advanced undergraduate physics course. Many physics students get very little more than an introduction to the material out of the lecture and prefer to learn from the textbook and homework. The current set of notes covers a 3 quarter course at UCSD. with derivations and examples available behind hyperlinks. The notes for the last quarter should be considered to be a ﬁrst draft. Some students claim they cannot learn from the textbook and rely on lectures to get their basic understanding. The use of this needs to be expanded and would beneﬁt from better software tools. only limited additional audio and visual material is now available. • To present a complex subject to students in several diﬀerent ways so that each student can use the learning techniques best suited to that individual. An important aspect of the design of the notes is to maintain a concise basic treatment of the physics. to have very detailed derivations. Another important aspect is audio discussion of important equations and drawings. One quarter is not suﬃcient to optimize the course material. It is my personal teaching experience that upper division physics students learn in diﬀerent ways. All of the standard software tools and information formats are usable from html. While a complete set of html based notes has been produced. not fully met at this time. this format will allow more examples than are practical in a textbook. LaTeX has the ability to
. • To produce course material that might be appropriate for distance learning or selfpaced courses in the future. The browser is able to concentrate on an equation while hearing about the details instead of having to go back an forth between text and equation. the experiment is in progress. Quantum Physics at UCSD. It is my goal. while others prefer a concise discussion largely based on equations. At this time. Every computer can access this format using Internet browsers. • To make use of some simple multimedia technology to enhance the class notes as a learning tool compared to a conventional textbook. Modern media have conditioned the students of today in a way that is often detrimental to learning complex subjects from either a lecture or a textbook. from the beginning of Quantum Mechanics to the quantization of the electromagnetic ﬁeld and the Dirac equation. This has not proved to be a limitation so far since native html can be included. Because of the heavy use of complex equations in this course. I chose to use html and the worldwide web as the primary delivery tool for enhanced class notes. • To get some experience with the use of multimedia technologies in teaching advanced courses. The experiment has several goals. Some prefer a rather verbose exposition of the material in the text.
Projects could be worked on in groups or individually. Advanced classes with small numbers of students could be taught based on notes. for review. I will plan to decrease the formal lecture time and add lab or discussion session time. Instructors would be available to answer questions and give suggestions. The primary teaching though probably still works best at the blackboard. Similar sessions would be possible at a distance. with students working moving at their own pace using computers. The LaTeX2html translator functions well enough for the conversion. The formal lecture could be taped and available in bite size pieces inside the lecture notes. Projecting the notes can be very useful in lecture for introductions.17 produce high quality equations and input is fast compared to other options. Classes could be oﬀered more often than is currently feasible. Jim Branson
. and for quick looks at derivations. with the notes fully prepared. In a future class. One thing that our classrooms really don’t facilitate is switching from one mode to the other. with less instructor support than is usual.
and everything else behave in exactly the same way. basic Atomic Theory. neutrons. photons. Einstein introduced Special Relativity which was compatible with Maxwell’s equations but changed our understanding of spacetime and modiﬁed Mechanics. deBroglie derived the wavelength (See section 2.4) for particles.5) of photons.
0. This deBroglie wavelength formula p relates the wave property λ to the particle property p. electrons. between wave frequency and particle energy satisﬁed.3
Probability Amplitudes
In Quantum Mechanics. and neutrons has been observed (see the pictures) and used to study crystal structure. but we always detect an integer number of photons with the Planck’s relation. electrons. There were problems with classical physics. exhibiting wavelike diﬀraction yet detection of an integer number of particles and satisfying λ = h . Much later. t) = ei(k·x−ωt) = ei(p·x−Et)/¯
. based on Newtonian Mechanics and Maxwell’s equations of Electricity and Magnetism described nature as we knew it. and eventually with the diﬀraction of all kinds of particles.18
0
0. E = hν. the problems led to the development of Quantum Mechanics in which all particles are understood to have both wave and a particle behavior. To understand the experimental input in a simpliﬁed way. Planck hypothesized that EM energy was always emitted in quanta E = hν = hω ¯ to solve the Black Body problem.2
Thought Experiments on Diﬀraction
Diﬀraction (See section 2) of photons. we consider some thought experiments on the diﬀraction (See section 2. and bullets through two slits. classical physics. (See section 1) including Black Body Radiation. Around that time.
0. show a diﬀraction pattern exactly as predicted by the theory of EM waves. For example. Compton Scattering. Statistical Mechanics was also a well developed discipline describing systems with a large number of degrees of freedom. Many things remained unexplained. h λ= p Ultimately. Electrons.1
Course Summary
Problems with Classical Physics
Around the beginning of the 20th century. which make up all electromagnetic waves. atomic structure was rich and quite mysterious.
h ψ(x. the Photoelectric eﬀect. While the electron as a constituent of atoms had been found. we understand this waveparticle duality using (complex) probability amplitudes (See section 3) which satisfy a wave equation.
t). In fact we recognize the wave property that. The Heisenberg Uncertainty Principle (See section 4. 2 Pdetector = ψ1 + ψ2  Quantum Mechanics completely changes our view of the world. φ(p). We can describe the state of a particle either in position space with ψ(x) or in momentum space with φ(p).) Similarly we can compute the coeﬃcient for each momentum 1 φ(p) = √ 2π¯ h
∞ h ψ(x)e−ipx/¯ dx.19 The probability to ﬁnd a particle at a position x at some time t is the absolute square of the probability amplitude ψ(x. P (p) = φ(p)2 We will show that wave packets like these behave correctly in the classical limit. We can build up localized wave packets that represent single particles(See section 4.4
Wave Packets and Uncertainty
(pc)2 + (mc2 )2 is the
The probability amplitude for a free particle with momentum p and energy E = complex wave function h ψfree particle (x. we add the probability amplitude to get to the detector through slit 1 to the amplitude to get to the detector through slit 2 and take the absolute square. vindicating the choice we made for ψfree particle (x. t)2 To compute the probability to ﬁnd an electron at our thought experiment detector. are actually the state function of the particle in momentum space.
0. P (x. to have exactly one frequency. t) = ei(p·x−Et)/¯ . Instead of a deterministic world. Quantum Mechanics will require us to use the mathematics of operators. t) = ψ(x.3) is a property of waves that we can deduce from our study of localized wave packets. a wave must be spread out over space. h ¯ ΔpΔx ≥ 2
. vector spaces.1) by adding up these free particle wave functions (with some coeﬃcients). t) = √ 2π¯ h
h φ(p)ei(px−Et)/¯ dp −∞
(We have moved to one dimension for simplicity.
+∞
1 ψ(x. Fourier Transforms. −∞
These coeﬃcients. We can use φ(p) to compute the probability distribution function for momentum.
Note that ψ2 = 1 everywhere so this does not represent a localized particle. We cannot even measure both the position and momentum of a particle (accurately) at the same time. we now have only probabilities. t). and much more.
we use the new concept of (linear) operators (See section 5). We determine the momentum and energy operators by requiring that.20 It shows that due to the wave nature of particles. we can estimate the ground state energy (and the size of) a Hydrogen atom very well from the uncertainty principle.
We have a shorthand notation for the expectation value of a variable v in the state ψ which is quite useful.
If the variable we wish to compute the expectation value of (like p) is not a simple function of x.5
Operators
The Schr¨dinger equation comes directly out of our understanding of wave packets. the normal way to compute the expectation value of f (x) is
∞ ∞
f (x) =
−∞
P (x)f (x)dx =
−∞
ψ ∗ (x)ψ(x)f (x)dx. If a particle is in the state ψ(x).6
Expectation Values
We can use operators to help us compute the expectation value (See section 5.3) of a physical variable. let its operator act on ψ(x)
∞
p =
−∞
ψ ∗ (x)p(op) ψ(x)dx. we get v times the same wave function. o
0. p(op) = x
h p(op) ei(p·x−Et)/¯ = x
h ¯ ∂ i ∂x
h E (op) ei(p·x−Et)/¯
h ¯ ∂ i(p·x−Et)/¯ h h e = px ei(p·x−Et)/¯ i ∂x ∂ E (op) = i¯ h ∂t ∂ i(p·x−Et)/¯ h h = i¯ e h = Eei(p·x−Et)/¯ ∂t
0. The diﬀerential equation which wave functions must satisfy is called the Schr¨dinger Equation. For example. when an operator for some variable v acts on our simple wavefunction. The next step in building up Quantum Mechanics is to determine how a wave function develops with time – particularly useful if a potential is applied.
We extend the notation from just expectation values to
∞
ψvφ ≡
−∞
ψ ∗ (x)v (op) φ(x)dx
. we cannot localize a particle into a small volume without increasing its energy. To get from wave o packets to a diﬀerential equation.
∞
ψvψ ≡
−∞
ψ ∗ (x)v (op) ψ(x)dx.
are an extremely important set. If we assume the equation separates. t)
p o where (dropping the (op) label) H = 2m + V (x) is the Hamiltonian operator.5) of two variables. t) = u(x)T (t). a continuous range of energies is allowed. In terms of operators. t) + V (x)ψ(x. t) = Eψ(x. the Schr¨dinger equation solutions which separate (See section 6. For bound states.
. in some sense.
0.
0.21 and ψφ ≡
−∞
∞
ψ ∗ (x)φ(x)dx
We use this shorthand Dirac BraKet notation a great deal.
2
0. t) = i¯ h 2m ∂t We will use it to solve many problems in this course. So the Schr¨dinger Equation is. x] ≡ px − xp = h ¯ . We will also use commutators to solve several important problems.8
The Schr¨dinger Equation o
Wave functions must satisfy the Schr¨dinger Equation (See section 6) which is actually a wave equation. ψ(x. Eigenvalues and Vector Spaces
For any given physical problem.7
Commutators
Operators (or variables in quantum mechanics) do not necessarily commute. o −¯ 2 2 h ∂ψ(x. i
Later we will learn to derive the uncertainty relation for two variables from their commutator. we get the two equations (in one dimension for simplicity) i¯ h ∂T (t) = E T (t) ∂t
Hu(x) = E u(x) The second equation is called the time independent Schr¨dinger equation. For states which are not bound. for example [p. there are o only solutions to that equation for some quantized set of energies Hui (x) = Ei ui (x). t) ∇ ψ(x. We can compute the commutator (See section 5. simply the statement (in operators) that the kinetic energy plus the potential energy equals the total energy.4) o (between time and space).9
Eigenfunctions. this can be written as Hψ(x.
h We can represent a state by giving the coeﬃcients in sum above. The arbitrary wavefunction φ would then be a vector in that space and could be represented by its coeﬃcients. There are usually an inﬁnite number of solutions. We can deﬁne the Hermitian conjugate (See section 7.. and Ei would be called an Eigenvalue. called degenerate eigenfunctions.22 The time independent Schr¨dinger equation is an example of an eigenvalue equation (See section 7. We can use the expansion in terms of energy eigenstates to compute many things.) We will assume that the eigenfunctions also form a complete set so that any wavefunction can be expanded in them.4). ψi ψj = δij (In the case of eigenfunctions with the same eigenvalue.) Since the ψi form an orthonormal. We can show that the eigenfunctions of Hermitian operators are orthogonal (and can be normalized).1).. we can must choose linear combinations which are orthogonal to each other. simply by computing the coeﬃcients αi at t = 0.. indicated by the index i here. They are called Hermitian operators (See section 7. we get back the same function ψi times some constant. t) = ψ(x)e−iEi t/¯
we can use these eigenstates to follow the time development of an arbitrary state φ ⎛ h⎞ α1 e−iE1 t/¯ −iE2 t/¯ h ⎜α e ⎟ φ(t) = ⎝ 2 −iE3 t/¯ ⎠ h α3 e .2) O† of the operator O by ψOψ = ψOψ = O† ψψ . (Note that ψp (x) = ei(px−Et)/¯ is −i(px−Et)/¯ h just an eigenfunction of the momentum operator and φx (p) = e is just an eigenfunction of the position operator (in pspace) so they also represent and expansion of the state in terms of eigenfunctions. The braket φψi can be thought of as a dot product between the arbitrary vector φ and one of the unit vectors. ⎛ ⎞ α1 ⎜ α2 ⎟ φ=⎝ ⎠ α3 . In this case ψi would be called and Eigenfunction. o Hψi (x) = Ei ψi (x) If we operate on ψi with H. since the time development of the energy eigenstates is very simple. they can be thought of as the unit vectors of a vector space (See section 7.3). Hermitian operators H have the property that H † = H. φ(x) =
i
αi ψi (x)
where the αi are coeﬃcients which can be easily computed (due to orthonormality) by αi = ψi φ . Operators for physical variables must have real eigenvalues. complete set. In particular. So now we have another way to represent a state (in addition to position space and momentum space).
..
h ψ(x.
the Schr¨dinger equation is o h ¯ 2 d2 un (x) = En un (x) 2m dx2 where we have anticipated that there will be many solutions indexed by n. and u(x) = cos(kx). we study the particle in a box (See section 7. In all other problems. So the energy eigenfunctions are given by a un (x) = C sin nπx a
nπx a
where we allow the overall constant C because it satisﬁes the diﬀerential equation. This example shows many of the features we will see for other bound state problems. We know four (only 2 linearly independent) functions which have a second derivative which is a constant times the same function: u(x) = eikx . so we require the boundary conditions Hun (x) = − u(0) = u(a) = 0. Since there is no potential inside.5) (in one dimension). This is just a particle (of mass m) which is free to move inside the walls of a box 0 < x < a.23
0.1).11
Piecewise Constant Potentials in One Dimension
We now study the physics of several simple potentials in one dimension.1. must be zero. We have one remaining task. The eigenstates should be normalized to represent one particle.
a
un un =
0
C ∗ sin
nπx a nπx C sin dx = C2 a a 2
2 a. we will have to pay more attention to this. it doesn’t change the physics. We solve the Schr¨dinger equation inside the box and realize that the probability o for the particle to be outside the box.
So the wave function will be normalized if we choose C = un (x) =
nπx 2 sin a a
We can always multiply by any complex number of magnitude 1.
0. The sine function is always zero at x = 0 and none of the others are. The one diﬀerence is that. To make the sine function zero at x = a we need ka = nπ or k = nπ . u(x) = e−ikx . and hence the wavefunction there. for which the Schr¨dinger equation is o −¯ 2 d2 u(x) h + V u(x) = Eu(x) 2m dx2
. but which cannot penetrate the walls. The wave function must be continuous though. 2ma2 Only quantized energies are allowed when we solve this bound state problem. we ﬁnd that o En =
h n2 π 2 ¯ 2 . we did not need to keep the ﬁrst derivative of the wavefunction continuous. but. We represent that by a potential which is zero inside the box and inﬁnite outside. First a series of piecewise constant potentials (See section 8. Plugging sin back into the Schr¨dinger equation.10
A Particle in a Box
As a concrete illustration of these ideas. u(x) = sin(kx). because of an inﬁnite change in the potential at the walls of the box.
E = −V0 + h n2 π 2 ¯ 2 8ma2
This type of behavior is exhibited by electrons scattering from atoms. It is found that the probability to be transmitted goes to 1 for some particular energies. barrier penetration is an important quantum phenomenon.
.24 or d2 u(x) 2m + 2 (E − V )u(x) = 0 dx2 h ¯ and the general solution. with k = 2m(E−V ) . for the case where the particle is not bound E > 0. we calculate the probability the a particle of energy E is reﬂected by a potential step (See section 8. Nevertheless. Assuming a beam of particles incident from the left. Classically the probability to be transmitted would be zero since the particle is energetically excluded from being inside the barrier.1. for E > V . Third we study the square potential barrier (See section 8. The Quantum calculation gives the probability to be transmitted through the barrier to be T 2 = (2kκ)2 4kκ 2 −4κa →( 2 ) e 2 + κ2 )2 sinh2 (2κa) + (2kκ)2 k + κ2 (k
2m(V0 −E) 2mE where k = and κ = . At some energies the scattering probability goes to zero.2) of height V0 : PR = current j =
h ¯ ∗ du 2im [u dx √ √ √E−√E−V0 E+ E−V0
2
. we need to match solutions in the three regions at the boundaries at x = ±a.1.3) square potential well (V (x) = −V0 for −a < x < a and V (x) = 0 elsewhere).4) case in which E < 0. Study of this expression shows that the probability to be h2 ¯ h2 ¯ transmitted decreases as the barrier get higher or wider. First. Here we need to solve a transcendental equation to determine the bound state energies. u(x) = Aeκx + Be−κx with κ = 2m(V2−E) .1.
We also study the square well for the bound state (See section 8. for the case in which E < V0 . the probabilities to be transmitted or reﬂected are computed. E < V .1. can be written as either u(x) = Aeikx + Be−ikx or u(x) = A sin(kx) + B cos(kx) . We will also need solutions for the classically forbidden regions where the total h2 ¯ energy is less than the potential energy.) The 1D scattering problems are often h ¯ analogous to problems where light is reﬂected or transmitted when it at the surface of glass. We also use this example to understand the probability
−
du∗ dx u].5) (V (x) = +V0 for −a < x < a and V (x) = 0 elsewhere).
Second we investigate the square potential well (See section 8. The number of bound states increases with the depth and the width of the well but there is always at least one bound state. (Both k and κ are positive real numbers. After some diﬃcult arithmetic.
periodic array of delta functions.13
Delta Function Potentials in One Dimension
The delta function potential (See section 8.
0. So the ground
e−mωx
2
/¯ h
. There are also bands of energies with solutions. 2¯ 2 h
Next we use two delta functions to model a molecule (See section 8.5). the solutions that are normalizable are Ceκx for x < 0 and Ce−κx for x > 0.
The energy eigenvalues are En = n+ 1 2 h ¯ ω. is just u0 (x) = mω π¯ h
1 4
/¯ h
.
. V (x) = −aV0 δ(x + d) − aV0 δ(x − d). The solution to this is a bit tricky but it comes down to cos(φ) = cos(ka) + 2maV0 sin(ka). A look at the wavefunction shows that the 2 delta function state can lower the kinetic energy compared to the state for one delta function.12
The Harmonic Oscillator in One Dimension
Next we solve for the energy eigenstates of the harmonic oscillator (See section 8. The excited state has more curvature than the atomic state so we would not expect molecular binding in that state.25
0. so this might be applicable to a crystal.
2
The energy eigenstates turn out to be a polynomial (in x) of degree n times e−mωx state. by reducing the curvature of the wavefunction.0 (or less than 1). Making u(x) continuous and its ﬁrst derivative have a discontinuity computed from the Schr¨dinger equation at x = 0. gives us exactly one bound state with o E=− ma2 V02 . h ¯ 2k
Since the right hand side of the equation can be bigger than 1. Since the bound state has negative energy. properly normalized. First we solve the problem with one attractive delta function V (x) = −aV0 δ(x).4).
We will later return the harmonic oscillator to solve the problem by operator methods.
∞
V (x) = −aV0
n=−∞
δ(x − na)
This has a inﬁnite. indicating that the molecule would be bound. Solving this problem by matching wave functions at the boundaries at ±d. is a model of a solid (See section 8.3) is a very useful one to make simple models of molecules and solids. there are regions of ¯ 2 k2 E = h2m which do not have solutions. we ﬁnd again transcendental equations for two bound state energies. Our ﬁnal 1D potential. where we have eliminated the spring constant k by using the classical oscillator frequency ω =
k m.2) potential V (x) = 1 1 2 2 2 2 kx = 2 mω x . These energy bands are seen in crystals (like Si). The ground state energy is more negative than that for one delta function.
A] = hω[A† A.14
Harmonic Oscillator Solution with Operators
We write the
We can solve the harmonic oscillator problem using operator methods (See section 9). h h This says that (Aun ) is an eigenfunction of H with eigenvalue (En − ¯ ω) so it lowers the energy by h ¯ ω. Since the energy must be positive for this Hamiltonian. A]un = −¯ ωAun which h rearranges to the eigenvalue equation H(Aun ) = (En − ¯ ω)(Aun ). We can travel up h 2h and down the energy ladder using A† and A. x= p = −i h ¯ (A + A† ) 2mω m¯ ω h (A − A† ) 2
. The energy eigenvalues are therefore h En = A little more computation shows that Aun = and that A† un = n+ √ 1 2 h ¯ ω. always in steps of ¯ ω. the lowering must stop somewhere.
nun−1
√ n + 1un+1 . Similarly. A† ] = i (−[x. H= We compute the commutators [A. at the ground state.26
0. we get [H. A] to the eigenfunction un . This allows us to compute the ground state energy like this 1 1 h ¯ Hu0 = hω(A† A + )u0 = ¯ ωu0 2 2 showing that the ground state energy is 1 ¯ ω. A] = hω[A† . p] + [p. A† raises the energy by ¯ ω. A† ] = hω[A† A. where we will have Au0 = 0. A† ] = hωA† [A.
These formulas are useful for all kinds of computations within the important harmonic oscillator system. Hamiltonian in terms of the operator A≡ . A]A = −¯ ωA ¯ ¯ h [H. A† ] = hωA† ¯ ¯ ¯ If we apply the the commutator [H. Both p and x can be written in terms of A and A† . x]) = 1 2¯ h mω p x + i√ 2¯ h 2m¯ ω h
1 1 p2 + mω 2 x2 = hω(A† A + ) ¯ 2m 2 2
[H.
A]ψ + ψ dt h ¯ ∂t ψ (Most operators we use don’t have explicit time dependence so the second term is usually zero.
. ∂A i d ψ ψAψ = ψ[H. For example. In some cases we can calculate the actual operator from the power series for the exponential. It is usually a symmetry of the H that leads to a commuting operator and hence an additional constant of the motion. we get o
h h h h ψ(t)Bψ(t) = e−iHt/¯ ψ(0)Be−iHt/¯ ψ(0) = ψ(0)eiHt/¯ Be−iHt/¯ ψ(0) .27
0. Again we use operator methods to calculate the time derivative of an expectation value (See section 10.
We use operator methods to compute the uncertainty relationship between noncommuting variables (See section 10. h ∂t
h ψ(t) = e−iHt/¯ ψ(t = 0) h This implies that e−iHt/¯ is the time development operator. We can use this to show that in Quantum mechanics the expectation values for p and x behave as we would expect from Newtonian mechanics (Ehrenfest Theorem). i i p2 dx = [H.6) in which the operators develop with time while the states do not change.3) i (ΔA)(ΔB) ≥ [A.5) by solving the equation i¯ ∂ψ = Hψ. h h In the Heisenberg picture the operator B(t) = eiHt/¯ Be−iHt/¯ . p] = dt h ¯ h ¯ [V (x). There is the alternate Heisenberg picture (See section 10. The energy eigenfunctions can also be (simultaneous) eigenfunctions of the commuting operator A.4). B] 2 which gives the result we deduced from wave packets for p and x.
h e−iHt/¯ =
(−iHt/¯ )n h n! n=0
∞
We have been working in what is called the Schr¨dinger picture in which the wavefunctions (or states) o develop with time.) This again shows the importance of the Hamiltonian operator for time development. h ¯ d ] i dx =− p m dV (x) dx
Any operator A that commutes with the Hamiltonian has a time independent expectation value. x] = [ . if we wish to compute the expectation value of the operator B as a function of time in the usual Schr¨dinger picture.15
More Fun with Operators
We ﬁnd the time development operator (See section 10. x] = dt h ¯ h ¯ 2m dp i i = [H.
The extension to two diﬀerent particles and to three dimensions (See section 11) is straightforward. Similarly. z(2) ] = i while [p(1)x . with no external potential. The only things that don’t commute are a coordinate with its momentum. x(2) )
−¯ 2 2 h −¯ 2 2 h ∇(1) + ∇ + V (x(1) . we will show that rotational symmetry implies conservation of angular momentum. or we may write states in which the particles are correlated.3) made in classical mechanics r ≡ r1 − r2 m1 r1 + m2 r2 R≡ m1 + m2 and reduce the problem to the CM moving like a free particle H= M = m1 + m2 −¯ 2 2 h ∇ 2M R plus one potential problem in 3 dimensions with the usual reduced mass. p2 p2 1 + 2 + V (r1 − r2 ) 2m 2m we can make the usual transformation to the center of mass (See section 11. h ¯ [p(2)z . H= 1 1 1 + = μ m1 m2 h ¯2 2 ∇ + V (r) 2μ r So we are now left with a 3D problem to solve (3 variables instead of 6). and remains invariant under the translation x → x + a.28
0. We may write states for two particles which are uncorrelated. We can show that this translational symmetry implies conservation of total momentum. y(2) ] = 0. for example. H=−
. The Hamiltonian for two particles in 3 dimensions simply becomes H= −¯ 2 h 2m(1) ∂2 ∂2 ∂2 2 + ∂y 2 + ∂z 2 ∂x(1) (1) (1) H= + −¯ 2 h 2m(2) ∂2 ∂2 ∂2 2 + ∂y 2 + ∂z 2 ∂x(2) (2) (2) + V (x(1) . H= −¯ 2 2 h −¯ 2 2 h ∇(1) + ∇ + V (x(1) − x(2) ) 2m(1) 2m(2) (1)
the Hamiltonian has a translational symmetry.16
Two Particles in 3 Dimensions
So far we have been working with states of just one particle in one dimension. For two particles interacting through a potential that depends only on diﬀerence on the coordinates. x(2) ] = [p(2)z . like u0 (x(1) )u3 (x(2) ). The coordinates and momenta of diﬀerent particles and of the additional dimensions commute with each other as we might expect from classical physics. x(2) ) 2m(1) 2m(2) (1)
If two particles interact with each other. and that time symmetry implies conservation of energy.
Lets call the operator that interchanges electron1 and electron2 P12 . operators commute with H. it takes three coordinates to give the location of a particle in 3D. [H. Electrons. In classical physics. We can use this to model White Dwarfs or Neutron Stars.
0. we are ﬁnding that it takes three quantum numbers to label and energy eigenstate (not including spin).
0. that the possible eigenvalues are ±1. P12 ] = 0 So we can make our energy eigenstates also eigenstates of P12 . In quantum mechanics.18
Some 3D Problems Separable in Cartesian Coordinates
We begin our study of Quantum Mechanics in 3 dimensions with a few simple cases of problems that can be separated in Cartesian coordinates (See section 12).1) V (r). It is a law of physics that spin 1 particles 2 called fermions (like electrons) always are antisymmetric under interchange. while particles with integer spin called bosons (like photons) always are symmetric under interchange.19
Angular Momentum
For the common problem of central potentials (See section 13. Again. One nice example of separation of variable in Cartesian coordinates is the 3D harmonic oscillator 1 V (r) = mω 2 r2 2 which has energies which depend on three quantum numbers. for example. This is possible when the Hamiltonian can be written H = Hx + H y + H z . are indistinguishable from each other so we must have a symmetry of the Hamiltonian under interchange (See section 11. Antisymmetry under interchange leads to the Pauli exclusion principle that no two electrons (for example) can be in the same state. [H. We investigate the eﬀect of the Pauli exclusion principle by ﬁlling our 3D box with identical fermions which must all be in diﬀerent states. Ly ] = 0
. Its easy to see (by operating on an eigenstate twice with P12 ). Another problem that separates is the particle in a 3D box. L = x × p. energies depend on three quantum numbers π2 ¯ 2 h n2 + n2 + n2 Enx ny nz = y z 2mL2 x for a cubic box of side L. Lz ] = [H. Lx ] = [H.29
0.4) of any pair of electrons.17
Identical Particles
Identical particles present us with another symmetry in nature. Enx ny nz = nx + ny + nz + 3 2 h ¯ω
It really behaves like 3 independent one dimensional harmonic oscillators. we use the obvious rotational symmetry to ﬁnd that the angular momentum.
The Y
m (θ. Lz ] = 0 We chose our two operators to be L2 and Lz . With this separation we expect (anticipating the angular solution a bit) uE (r) = RE (r)Y will be a solution. Ly ] = 0 We want to ﬁnd two mutually commuting operators which commute with H. φ) m (θ. Some computation reveals that we can write p2 = 1 L2 + (r · p)2 − i¯ r · p . φ)
so the radial equation becomes −¯ 2 h 2μ 1 r2 r ∂ ∂r
2
+
( + 1) 1 ∂ − RE (r) + V (r)RE (r) = ERE (r) r ∂r r2
We must come back to this equation for each V (r) which we want to solve. The operators that raise and lower the z component of angular momentum are L± = Lx ± iLy L± Y
m
=h ¯
( + 1) − m(m ± 1)Y
(m±1)
We derive the functional form of the Spherical Harmonics Y the angular momentum operators. h r2
With this the kinetic energy part of our equation will only have derivatives in r assuming that we have eigenstates of L2 . We ﬁnd that angular momentum is quantized. φ)
using the diﬀerential form of
. so we turn to L2 = L2 + L2 + L2 which does commute with each component of L.
m (θ. φ) m (θ. φ)
= m¯ Y h
m (θ. [Lx .30 but they do not commute with each other. φ)
m (θ. φ)
will be eigenfunctions of L2 L2 Y
m (θ. Lz Y L2 Y
m (θ. We solve the angular part of the problem in general using angular momentum operators. −¯ 2 h 2μ 1 r2 r ∂ ∂r
2
+
L2 1 ∂ − 2 uE (r) + V (r)uE (r) = EuE (r) r ∂r ¯ r2 h
The Schr¨dinger equation thus separates into an angular part (the L2 term) and a radial part o (the rest). φ)
= ( + 1)¯ 2 Y h
m (θ. φ)
= ( + 1)¯ 2 Y h
with and m integers satisfying the condition − ≤ m ≤ . x y z [L2 .
The solutions are the spherical Bessel and spherical Neumann functions (See section 14.31
0. They are therefore used in scattering problems as the incoming and outgoing states.
. The diagram below shows the lowest energy bound states of Hydrogen and their typical decays. then ﬁnding the behavior at small r. Z 2 α2 mc2 En = − 2n2 Here n is called the principle quantum number and it is given by n = nr + + 1 where nr is the number of nodes in the radial wavefunction. We compute several of the lowest energy eigenstates. h
(1)
(ρ) = j (ρ) + in (ρ) = (−ρ)
1 d ρ dρ
sin ρ − i cos ρ i → − ei(ρ− ρ ρ
π 2 )
We use these solutions to do a partial wave analysis of scattering. The linear combination of these which falls oﬀ properly at large r is called the Hankel function of the ﬁrst type.1) in a constant potential are important since they are the solutions for large r in potentials of limitted range. solve for bound states of an inﬁnite spherical well (a spherical “box”). It is an odd feature of Hydrogen that a radial excitation and an angular excitation have the same energy. giving us h2 ¯ our energy eigenvalue condition. The ground state of Hydrogen is ψ100 and has energy of 13. φ) is described by three integer quantum numbers with the requirements that n ≥ 1. To keep the wavefunction normalizable the power series must terminate.21
Hydrogen
The Hydrogen (Coulomb potential) radial equation (See section 15) is solved by ﬁnding the behavior at large r. So a Hydrogen energy eigenstate ψn m (x) = Rn (r)Y m (θ. < n and also an integer.6 eV.20
Solutions to the Radial Equation for Constant Potentials
Solutions to the radial equation (See section 14.
0. j (ρ) = (−ρ) 1 d ρ dρ 1 d ρ dρ sin(ρ − sin ρ → ρ ρ
π 2 )
n (ρ) = −(−ρ)
− cos(ρ − cos ρ → ρ ρ
π 2 )
where ρ = kr. then using a power series solution to get
∞
R(ρ) = ρ
k=0
ak ρk e−ρ/2
with ρ = −8μE r.3). and solve for scattering from a spherical potential well. and −l ≤ m ≤ . solve for bound states of a spherical potential well.
22
Solution of the 3D HO Problem in Spherical Coordinates
As and example of another problem with spherical symmetry.32
0.23
Matrix Representation of Operators and States
We may deﬁne the components of a state vector ψ as the projections of the state on a complete. This gives exactly the same set of eigenenergies as we got in the Cartesian solution but the eigenstates are now states of deﬁnite total angular momentum and z component of angular momentum. like the eigenfunctions of a Hermitian operator. ψi ψ ≡ =
i
ui ψ ψi ui
. We have already solved this problem in Cartesian coordinates. The eigenenergies are E= 2nr + + 3 2 h ¯ω
where nr is the number of nodes in the radial wave function and is the total angular momentum quantum number. Now we use spherical coordinates and angular momentum eigenfunctions. orthonormal set of states.
0. we solve the 3D symmetric harmonic oscillator (See section 16) problem.
.... The states are often (nearly) degenerate and therefore should be treated as a group for practical reasons... s = 1.. The rotation operators (See section 17.. Quantum Mechanics problems can be solved using the matrix representation operators and states.. There are both practical and theoretical reasons why this set of states is separated from the states with diﬀerent total angular momentum quantum numbers.. .6) (symmetry operators) are given by
h Rz (θz ) = eiθz Lz /¯ h Rx (θx ) = eiθx Lx /¯ h Ry (θy ) = eiθy Ly /¯
for the diﬀerential form or the matrix form of the operators. Also. ⎞ ⎛ O11 (Oψ)1 ⎜ (Oψ)2 ⎟ ⎜ O21 ⎜ ⎟ ⎜ ⎜ ...1).. For = 1 these are 3X3 (unitary) matrices.
The product of operators is the product of matrices. For example the diﬀerent m states for = 1 will be represented by a 3 component vector and the angular momentum operators (See section 17... but of course would act on a diﬀerent vector space..33 Similarly.. ..... . ⎟ ⎜ .
0..
.. We write our 3 component vectors as follows. ⎝ ⎠ ⎝ Oi1 (Oψ)i . With these deﬁnitions. ⎟ = ⎜ . O2j .. .. O1j ....2) represented by 3X3 matrices... . We use them when we need to redeﬁne the direction of our coordinate axes. we may deﬁne the matrix element of an operator in terms of a pair of those orthonormal basis states Oij ≡ ui Ouj ..24
A Study of
= 1 Operators and Eigenfunctions
The set of states with the same total angular momentum and the angular momentum operators which act on them are often represented by vectors and matrices. The components of the vectors represent diﬀerent quantities and hence transform quite diﬀerently. Oij . . .. Operators which don’t commute are represented by matrices that don’t commute. ⎟ ⎜ ψ2 ⎟ ⎟⎜ ⎟ .. Rotations of the angular momentum states are not the same as rotations of vectors in 3 space.. ⎛ O12 O22 .... Oi2 .. An operator acting on a state is a matrix times a vector. a rotation of the coordinate axes will not change the total angular momentum quantum number so the rotation operator works within this group of states. ⎟ ⎠⎝ ⎠ ψj . The “vectors” we are using for angular momentum actually should be called spinors when we refer to their properties under rotations and Lorentz boosts. ⎛ ⎞ ⎛ ⎞ ⎛ 0 1 0 0 1 0 1 0 h ¯ ⎝ h ¯ ⎝ 1 0 1⎠ Ly = √ −1 0 1 ⎠ Lz = h ⎝ 0 0 ¯ Lx = √ 2 0 1 0 2i 0 −1 0 0 0 ⎞ 0 0 ⎠ −1
The same matrices also represent spin 1... (See section 17. . ⎞⎛ ⎞ ψ1 . ⎞ ψ+ ψ = ⎝ ψ0 ⎠ ψ− ⎛ The matrices representing the angular momentum operators for = 1 are as follows.
σj ] = 2 σi = σx σy + σy σx = σx σz + σz σx {σi .25
Spin 1/2 and other 2 State Systems
The angular momentum algebra deﬁned by the commutation relations between the operators requires that the total angular momentum quantum number must either be an integer or a half integer. σj } = =
σz σy + σy σz = 0 2δij
The last two lines state that the Pauli matrices anticommute.
0. which have the following properties. The half integer possibility is used to represent the internal angular momentum of some particles. with z component of angular momentum + h . not just the particle’s momentum. The half integer possibility was not useful for orbital angular momentum because there was no corresponding (single valued) spherical harmonic function to represent the amplitude for a particle to be at some position. σi . The σ matrices are the Hermitian. It is common to deﬁne the Pauli Matrices. Note that the momentum operator will now include momentum in the ﬁeld.26
Quantum Mechanics in an Electromagnetic Field
The classical Hamiltonian for a particle in an Electromagnetic ﬁeld is H= 1 e p+ A 2m c
2
− eφ
where e is deﬁned to be a positive number. p is the variable conjugate to r and is related to the velocity by p = mv − e A. c
. As this Hamiltonian is written. 2 h ¯ σ 2 0 −i i 0 2i 1
ijk σk
σz =
1 0
0 −1
[σi . The corresponding spin operators are 2 1 Sx = h ¯ 2 0 1 1 0 Sy = h ¯ 2 0 i −i 0 Sz = h ¯ 2 1 0 0 −1
These satisfy the usual commutation relations from which we derived the properties of angular momentum operators. This Hamiltonian gives the correct Lorentz force law. Si S σx = 0 1 1 0 σy ≡ = = h ¯ σi . Any 2 by 2 matrix can be written as a linear combination of the σ matrices and the identity. The simplest and most important case is spin onehalf (See section 17.34
0. Traceless matrices of dimension 2. and 2 0 0 ¯ spin down .8). There are just two possible states 1 ¯ with diﬀerent z components of spin: spin up . with − h .
t) ψ(r. the dominant additional term is HB = e B · L = −μ · B. the magnetic moment due to the electron’s orbital angular momentum. t) φ → φ+ c ∂t The local phase symmetry requires that Electromagnetism exist and have a gauge symmetry so that we can keep the Schr¨dinger Equation invariant under this phase transformation.35 In Quantum Mechanics. This problem can be simpliﬁed using a few diﬀerent symmetry operators. ¯ k is the conserved momentum along the ﬁeld direction which h can take on any value. eﬀectively. for atoms. We work the example of a plasma in a constant magnetic ﬁeld. To compensate for this change. we need to also make a gauge transformation (See section 19. n+ + me c 2 2me which depends on 2 quantum numbers. In this symmetry we change the phase of the (electron) wavefunction by a diﬀerent amount everywhere in spacetime. o
. This is. They all must go together like this. e p→p+ A c Starting from the above Hamiltonian. the momentum operator is replaced (See section 19) in the same way to include the eﬀects of magnetic ﬁelds and eventually radiation. 2mc
e where μ = − 2mc L. We work it two diﬀerent ways: in one it reduces to the radial equation for the Hydrogen atom.3) of the electromagnetic potentials. t) 1 ∂f (r. So.
0.
The other terms can be important if a state is spread over a region much larger than an atom. in the other it reduces to the Harmonic Oscillator equation. t) → e−i hc f (r. A charged particle in the plasma has the following energy spectrum eB¯ h 1 h ¯ 2 k2 En = . plus some additional terms which are very small for atoms in ﬁelds realizable in the laboratory. e2 e −¯ 2 2 h r2 B 2 − (r · B)2 ψ = (E + eφ)ψ ∇ ψ+ B · Lψ + 2m 2mc 8mc2 This has the familiar eﬀect of a magnetic moment parallel to the angular momentum vector. we derive the Hamiltonian for a particle in a constant magnetic ﬁeld. n is an integer dealing with the state in x and y. t) e
A → A − ∇f (r.
¯ ψ(r.27
Local Phase Symmetry in Quantum Mechanics and the Gauge Symmetry
There is a symmetry in physics which we might call the Local Phase Symmetry in quantum mechanics. showing that these two problems we can solve are somehow equivalent.
r
f (r) =
r0
dr · A.
We use this to show that the magnetic ﬂux enclosed by a superconductor is quantized. → ψ1 e → ψ2 e =
e −i hc ¯ 1 e −i hc ¯ 2 e −i hc ¯
dr·A
ψ1 ψ2 ψ
dr·A
ψ1 e
−i eΦ hc ¯
dr·A
2
+ ψ2 e
The relative phase from the two slits depends on the ﬂux between the slits. the wavefunctions must change. in ﬁeld free regions.
. By varying the B ﬁeld. the amplitudes from the two slits interfere ψ = ψ1 + ψ2 . When we change the B ﬁeld. Let’s start with B = 0 and A = 0 everywhere. The Aharanov B¨hm Eﬀect brings us back to the two slit diﬀraction experiment but adds magnetic o ﬁelds.
electron gun
1111111 0000000 1111111 0000000 flux 1111111 0000000 1111111 0000000
screen
The electron beams travel through two slits in ﬁeld free regions but we have the ability to vary a magnetic ﬁeld enclosed by the path of the electrons.36 We exploit the gauge symmetry in EM to show that. we will shift the diﬀraction pattern even though B = 0 along the whole path of the electrons. the function f can be simply equal to a line integral of the vector potential (if we pick the right gauge). We also show that magnetic ﬁelds can be used to change interference eﬀects in quantum mechanics. At the screen.
We will show that the total angular momentum quantum number takes on every value in the range  1 − 2 ≤ j ≤ 1 + 2. L1 and L2 to get a total angular momentum J.
l2 l2 l1 l1 . For example if I add two = 2 states together. 2.l 2 l2 l1 + l 2
The length of the resulting vector is somewhere between the diﬀerence of their magnitudes and the sum of their magnitudes. The states of deﬁnite total angular momentum with quantum numbers j and m. When combining states of identical particles. since we don’t know which direction the vectors are pointing. the highest total angular momentum state.28
Addition of Angular Momentum
It is often required to add angular momentum from two (or more) sources (See section 20) together to get states of deﬁnite total angular momentum. The total number of states is always preserved. will always be symmetric under interchange. lets assume we are adding the orbital angular momentum from two electrons.37
0. This almost has to be true if there is spherical symmetry to the problem. 3 and 4. As an example. in the absence of external ﬁelds. The general expansion is called the ClebschGordan series: ψjm =
m1 m2 1 m1 2 m2 jm 1 2
Y
1 m1
Y
2 m2
or in terms of the ket vectors jm
1 2
=
m1 m2
1 m1 2 m2 jm 1 2
 1 m1 2 m2
The ClebschGordan coeﬃcients are tabulated although we will compute many of them ourselves. We are adding two quantum vectors. s = s1 +s2 . We can understand this qualitatively in the vector model pictured below. There are 25 product states since each = 2 state
. 1. The symmetry under interchange will alternate as j is reduced. For example. can be written in terms of products of the individual states (like electron 1 is in this state AND electron 2 is in that state). I get total angular momentum states with j = 0. the energy eigenstates of Hydrogen (including all the ﬁne structure eﬀects) are also eigenstates of total angular momentum.
We will use addition of angular momentum to: • Add the orbital angular momentum to the spin angular momentum for an electron in an atom J = L + S.38 has 5 diﬀerent possible ms.. • Add the nuclear spin to the total atomic angular momentum F = J + I. we compute the correco tions to the energies and eigenfunctions. • Write the product of spherical harmonics in terms of a sum of spherical harmonics. By solving the Schr¨dinger equation at each order of the perturbation series. (2) are the zeroth. we may use a perturbation series. ψn = N φn +
k=n (1) (2) (0) (1) (2)
cnk φk
cnk = cnk + cnk + . (1). Check that against the sum of the number of states we have just listed. 5 ⊗ 5 = 9S ⊕ 7A ⊕ 5S ⊕ 3A ⊕ 1S where the numbers are the number of states in the multiplet. En = En + En + En + . (see section 21... We can use time independent perturbation theory (See section 21) to calculate corrections to the energy eigenvalues and eigenstates.1) We just give the ﬁrst few terms above. If the Schr¨dinger equation for the full problem o is (H0 + H1 )ψn = En ψn and we have already solved the eigenvalue problem for H0 . • Add the total angular momenta of two electrons together J = J1 + J2 . ﬁrst. En = φn H1 φn cnk = En =
(2) (1) φk H1 φn (0) (0) En −Ek  φk H1 φn 2 (0) (0) k=n En −Ek (1)
. and second order terms in the series. N is there to keep the wave function normalized but will not play an important role in our results. to expand both our energy eigenvalues and eigenstates in powers of the small perturbation.
0. where the superscript (0). • Add the spins of two particles together S = S1 + S2 . • Add the orbital angular momenta together for two electrons in an atom L = L1 + L2 ..4. • Add the total orbital angular momentum to the total spin angular momentum for a collection of electrons in an atom J = L + S.29
Time Independent Perturbation Theory
Assume we have already solved and an energy eigenvalue problem and now need to include an additional term in the Hamiltonian.
30
The Fine Structure of Hydrogen
We have solved the problem of a nonrelativistic. 3. 1. We know that it is in fact a combination of the orbital and spin g factors in a
. they can all be called relativistic corrections which are oﬀ order α2 compared to the Hydrogen energies we have calculated. The relativistic correction to the electron’s kinetic energy. spinless electron in a coulomb potential exactly. φ(j) Hφ(i) αi = En αj . Real Hydrogen atoms have several small corrections to this simple solution. Calculating these ﬁne structure eﬀects (See section 22) separately and summing them we ﬁnd that we get a nice cancellation yielding a simple formula. The correction due to a weak magnetic ﬁeld is found to be ΔE = ψn
jmj
eB (Lz + 2Sz ) ψn 2mc
jmj
=
e¯ B h 1 mj 1 ± 2mc 2 +1
is known as the Lande g Factor because the state splits as if it had this The factor 1 ± 2 1 +1 gyromagnetic ratio. Enlm =
(0) En
En 4n + 3− 2mc2 j+1 2
(0) 2
The correction depends only on the total angular quantum number and does not depend on so the states of diﬀerent total angular momentum split in energy but there is still a good deal of degeneracy. To handle this case. that the states of deﬁnite total angular momentum are the energy eigenstates and that the result depend on j. The external ﬁeld is very important since it breaks the spherical symmetry and splits degenerate states allowing us to understand Hydrogen through spectroscopy. 2. n n
i∈N
This is just the standard eigenvalue problem for the full Hamiltonian in the subspace of (nearly) degenerate states. The SpinOrbit correction. The “Darwin Term” correction to s states from Dirac equation. for a problem with spherical symmetry. We will use time independent perturbation theory is used to compute ﬁne structure and hyperﬁne corrections to Hydrogen energies.39 A problem arises in the case of degenerate states or nearly degenerate states. The energy denominator in the last equation above is small and the series does not converge. We also compute the Zeeman eﬀect in which an external magnetic ﬁeld is applied to Hydrogen. Degenerate state perturbation theory will be used for the Stark Eﬀect and for hyperﬁne splitting in Hydrogen.
0. as well as for many other calculations. If we say that electron spin is a relativistic eﬀect. It makes sense. we need to rediagonalize the full Hamiltonian in the subspace of nearly degenerate states.
We could diagonalize the 4 by 4 matrix for the perturbation to solve the problem or we can use what we know to pick the right states to start with. it is gp ≈ 5. as a perturbation. Enjmj
s
1 = − α2 mc2 2
1 1 α2 + 3 2 n n j+
1 2
−
3 4n
+ gL μB Bmj
Thus. The magnetic moment of the nucleus is μN = ZegN I 2MN c
where I is the nuclear spin vector. we will deﬁne the total angular momentum F = S + I. In essence. just as in the case of the L · S. It is in the states of deﬁnite f and mf that the hyperﬁne perturbation will be diagonal. We have assumed that the eﬀect of the ﬁeld is small compared to the ﬁne structure corrections. the nuclear gyromagnetic ratio is not just 2. We can write the full energy in a weak magnetic ﬁeld. the proton. in a weak ﬁeld. the total angular momentum states will be the right states because we can write the perturbation in terms of quantum numbers of those states. Again like the spin orbit interaction. It is called hyperﬁne me because it is also order α2 like the ﬁne structure corrections. For the proton. and the neutron have internal structure. All the states can be detected spectroscopically. Because the nucleus.
. we are doing degenerate state perturbation theory. 1 S·I n3 ¯ 2 h
(mc2 )gN
Now.40 state of deﬁnite j.31
Hyperﬁne Structure
The interaction between the spin of the nucleus and the angular momentum of the electron causes a further (hyperﬁne) splitting (See section 23) of atomic states. but it is smaller by a factor of about mp because of the mass dependence of the spin magnetic moment for particles. spinorbit interaction. on the order of 500 Gauss. In the strong ﬁeld limit we could use states of deﬁnite m and ms and calculate the eﬀects of the ﬁne structure. H1 + H2 .
0.56. In an intermediate strength ﬁeld. We computed the hyperﬁne contribution to the Hamiltonian for Hhf = 4 e S · B = (Zα)4 mc 3 m MN = 0 states.
S·I = ΔE =
1 1 3 3 F 2 − S 2 − I 2 = ¯ 2 f (f + 1) − − h 2 2 4 4 2 (Zα)4 3 m MN (mc2 )gN 1 n3 f (f + 1) − 3 2 . the the degeneracy is completely broken for the states ψnjmj s . the combination of the Hydrogen ﬁne structure Hamiltonian and the term to the B ﬁeld must be diagonalized on the set of states with the same principal quantum number n.
2 The transition between the two states gives rise to EM waves with λ = 21 cm.
2
0. We can estimate the ground state energy in ﬁrst order perturbation theory. the spin part of the state must be antisymmetric so s = 0 (as it always is for closed shells). For our zeroth order energy eigenstates.8 74. We will work out the eﬀect of an external B ﬁeld on the Hydrogen hyperﬁne states both in the strong ﬁeld and in the weak ﬁeld approximation. This is not very accurate.32
The Helium Atom
The Hamiltonian for Helium (See section 24) has the same terms as Hydrogen but has a large perturbation due to the repulsion between the two electrons. We can improve the estimate of the ground state energy using the variational principle. H= p2 Ze2 p2 Ze2 e2 1 + 2 − − + 2m 2m r1 r2 r1 − r2 
Note that the perturbation due to the repulsion between the two electrons is about the same size as the the rest of the Hamiltonian so ﬁrst order perturbation theory is unlikely to be accurate. 1. We also work the problem without a ﬁeld strength approximation.8 77. We can do this in some reasonable approximation by reducing the charge of the nucleus in the wavefunction (not in the Hamiltonian). we get a better estimate of the energy. using the electron repulsion term as a (very large) perturbation. The energy for two electrons in the (1s) state for Z = 2 is then 4α2 mc2 = 108.
Calculation 0th Order 1st Order perturbation theory 1st Order Variational Actual
Energy 108.38 78. Since the spatial state is symmetric. we will use product states of Hydrogen wavefunctions u(r1 . The main problem with our estimate from perturbation theory is that we are not accounting for changes in the wave function of the electrons due to screening.8 eV. r2 ) = φn1
1 m1
(r1 )φn2
2 m2
(r2 )
and ignore the perturbation.41 For the hydrogen ground state we are just adding two spin 1 particles so the possible values are f = 0. The Helium ground state has two electrons in the 1s level. The four energies are E E = = En00 + En00 − A¯ 2 h ± μB B 4 A¯ 2 h ± 4 A¯ 2 h 2
2
+ (μB B) . With the parameter Z ∗ . Two of the energy eigenstates mix in a way that also depends on B.975
Zwf n 2 2
27 16
. The always applicable intermediate ﬁeld strength result is that the four states have energies which depend on the strength of the B ﬁeld.
0. 5p. the spatial states are (usually) diﬀerent so they can be either symmetric or antisymmetric (under interchange of the two electrons). The ﬁrst exited state has the hydrogenic state content of (1s)(2s) and has s=1.42 Note that the variational calculation still uses ﬁrst order perturbation theory. For excited states. φ)2 = 4π
m=−
With all the states ﬁlled and the relative phases determined by the antisymmetry required by Pauli. So the triplet states are generally signiﬁcantly lower in energy than the corresponding spin singlet states. It just adds a variable parameter to the wavefunction which we use to minimize the energy. There is only one allowed (1s)2 state and it is the ground state.
. then the spin state is symmetric. 3d. We calculated the energy of this state. ⎤ ⎡ Z Ze2 p2 e2 ⎦ i ⎣ − ψ = Eψ. 2p. + 2m ri ri − rj  i=1 i>j We have seen that the coulomb repulsion between electrons is a very large correction in Helium and that the three body problem in quantum mechanics is only solved by approximation. 4s. The physics of closed shells and angular momentum enable us to make sense of even the most complex atoms.33
Atomic Physics
The Hamiltonian for an atom with Z electrons and protons (See section 25) has many terms representing the repulsion between each pair of electrons. When we have enough electrons to ﬁll a shell. say the 1s or 2p. Because of the screening. 2s. It turns out that the antisymmetric state has the electrons further apart so the repulsion is smaller and the energy is lower. This only works for the ground state and for other special states. We see that the atomic shells ﬁll up in the order 1s. 4p. 3p. 5s. Y m (θ. We’ll learn later that electromagnetic transitions which change spin are strongly suppressed causing the spin triplet (orthohelium) and the spin singlet states (parahelium) to have nearly separate decay chains. The resulting electron distribution is spherically symmetric because 2 +1 . s=1. This appears to be a strong spin dependent interaction but is actually just the eﬀect of the repulsion between the electrons having a big eﬀect depending on the symmetry of the spatial state and hence on the symmetry of the spin state. 3s. If the spatial state is antisymmetric. Electrons which are far away from the nucleus see less of the nuclear charge and shift r up in energy. the potential no longer has a pure 1 behavior. There is only one possible state representing a closed shell and the quantum numbers are s=0 =0 j=0 The closed shell screens the nuclear charge. the quantum numbers of the closed shell are determined. 4d.
known as Hund’s rules. if an 2 atom is two electrons short of a closed shell. As we add valence electrons we follow Hund’s rules to determine the ground state.) 3. ψHψ = 2EH + (RAB ) −
2
e2 e2 + ψ ψ RAB r12
The molecule can vibrate in the potential created when the shared electron binds the atoms together. there is overlap.s. a much larger energy. The eﬀect of screening increasing the energy of higher that the periodic table is not completely periodic. Molecules can rotate like classical rigid bodies subject to the constraint that angular momentum is quantized in units of ¯ . We get a great simpliﬁcation by treating nearly closed shells as a closed shell plus positively charged. 2. Remember. For example. this symmetry is that of the wavefunction of one electron around the two nuclei. The Pauli principle rather than the rule. The lowest energy wavefunction can be thought of as a (anti)symmetric linear combination of an electron in the ground state near nucleus A and the ground state near nucleus B ψ± r. h Erot = ( + 1)¯ 2 h h ¯2 m 1 1 L2 m α2 mc2 = ≈ ≈ E≈ eV = 2 2 I 2I 2M a0 M 2 M 1000
. 5d. It has two nuclei (A and B) 2 sharing one electron (1). pick the highest total angular momentum state j = +s otherwise pick the lowest j =  − s. The antisymmetric (antibonding) state has a small probability there. Its no wonder
A set of guidelines. 4f. spin 1 holes. Couple the valence electrons (or holes) to give maximum total spin. help us determine the quantum numbers for the ground states of atoms. and hence.) 1. states is clear.
0. e2 p2 e2 e2 H0 = e − − + 2m r1A r1B RAB RAB is the distance between the two nuclei. Now choose the state of maximum (subject to the Pauli principle. often determines everything here. we treat it as a closed shell plus two positive holes.34
Molecules
We can study simple molecules (See section 26) to understand the physical phenomena of molecules in general.43 6s.
The symmetric (bonding) state has a large probability for the electron to be found between nuclei. ψA and ψB are not orthogonal. 6p. giving rise to a harmonic oscillator energy spectrum. around nucleus A. We calculate the ground state energy using the Hydrogen states as a basis. If the shell is more than half full. The H2 molecule is also simple and its energy can be computed with the help of the previous calculation. The hydrogenic shells ﬁll up giving well deﬁned j = 0 states for the closed shells. The simplest molecule we can work with is the H+ ion. R = C± (R) [ψA ± ψB ] where ψA =
1 −r1A /a0 e πa3 0
is g. The space symmetric state will be the ground state.
The transition rate would be zero if energy is not conserved and inﬁnite if energy is exactly conserved. H= e 1 p+ A 2m c
2
+ V (r). In either case. then the vector potential terms in the Hamiltonian can be treated as a perturbation. the perturbation is V= e2 e A·p+ A2 . i¯ h ∂cn (t) ∂t =
k h Vnk (t)ck (t)ei(En −Ek )t/¯
Assuming that at t = 0 the quantum system starts out in some initial state φi . mc 2mc2
For most atomic decays. 2 2πVni dPn = δ(En − Ei + hω) Γi→n ≡ ¯ dt h ¯ This contains a delta function of energy conservation. we derive the transition rate in a harmonic potential of frequency ω.35
Time Dependent Perturbation Theory
We have used time independent perturbation theory to ﬁnd the energy shifts of states and to ﬁnd the change in energy eigenstates in the presence of a small perturbation. Both the decay of excited atomic states with the emission of radiation and the excitation of atoms with the absorption of radiation can be calculated.
.
0. We now consider the case of a perturbation V that is time dependent. The atomic problem is solved in the absence of EM waves. the A2 term can be neglected since it is much smaller than the A · p term. the delta function helps us do the integral simply. Such a perturbation can cause transitions between energy eigenstates. The delta function may seem strange. We derive an equation for the rate of change of the amplitude to be in the nth energy eigenstate.
t
1 cn (t) = i¯ h
0
eiωni t Vni (t )dt
An important case of a time dependent potential is a pure sinusoidal oscillating (harmonic) perturbation. With some calculation.36
Radiation in Atoms
The interaction of atoms with electromagnetic waves (See section 28) can be computed using time dependent perturbation theory. We can make sense of this if there is a distribution function of P (ω) of the perturbing potential or if there is a continuum of ﬁnal states that we need to integrate over. we derive the amplitude to be in a ﬁnal state φn .
In a gauge in which ∇ · A = 0.44
0. We can make up any time dependence from a linear combination of sine and cosine waves. We will calculate the rate of those transitions (See section 27).
We can assume that the atom remains at rest as a very good approximation. t) = A(r. ¯ we may write ﬁeld strength in terms of the number of photons N . Think of the EM ﬁeld as a harmonic oscillator at each frequency. there is a perturbation even with no applied ﬁeld (N = 0) VN =0 = VN =0 e
iωt
e 2π¯ c2 h e A·p = = mc mc ωV
1 2
e−i(k·r−ωt) ˆ · p
which can cause decays of atomic states. A(r. kx L = 2πnx ky L = 2πny kz L = 2πnz d n=
3
dnx = dny = dnz =
L 2π dkx L 2π dky L 2π dkz
L3 3 (2π)3 d k
=
Γtot =
Γi→n d n
V 3 (2π)3 d k 3
.45 An arbitrary EM ﬁeld can be Fourier analyzed to give a sum of components of deﬁnite frequency. A(r. If the ﬁeld is quantized (as we will later show) with photons of energy E = hω. t) = 2π¯ c2 h ωV
1 2
ˆ
√ i(k·r−ωt) √ Ne + N + 1e−i(k·r−ωt)
With this change. The energy in the ﬁeld is ω2 Energy = 2πc2 V A0 2 . Plugging this N = 0 ﬁeld into the ﬁrst order time dependent perturbation equations. Γi→n = (2π)2 e2  φn e−ik·r ˆ · pφi 2 δ(En − Ei + hω) ¯ m2 ωV
The absolute square of the time integral from perturbation theory yields the delta function of energy conservation. In time dependent perturbation theory. t) ≡ 2A0 cos(k · r − ωt). but. Applying periodic boundary conditions in a cubic volume V . the ﬁnal photon states must be carefully considered. In analogy to the √ √ quantum 1D harmonic oscillator we replace N by N + 1 in the raising operator case. The cosine term has been split into positive and negative exponentials. A(r. the integral over ﬁnal states can be done as indicated below. the positive exponential corresponds to the absorption of a photon and excitation of the atom and the negative exponential corresponds to the emission of a photon and decay of the atom to a lower energy state. the negative exponential corresponds to a raising operator for the ﬁeld and the positive exponential to a lowering operator. Consider the vector potential for one such component. we must sum over the allowed ﬁnal states. the decay rate for an atomic state can be computed. t) = 2π¯ c2 N h ωV 2π¯ c2 N h ωV
1 2
ˆ2 cos(k · r − ωt) ˆ ei(k·r−ωt) + e−i(k·r−ωt)
1 2
The direction of the ﬁeld is given by the unit polarization vector ˆ. which will later be justiﬁed with the quantization of the ﬁeld. To get the total decay rate.
summed over ﬁnal photon polarization and integrated over photon direction.
. where the integer q runs from 1 to +1. as might be expected from the uncertainty principle. This is the outcome of the WignerEckart theorem which states that the matrix element of a vector operator V q . other eﬀects can inﬂuence measured widths. ±1 Δs = 0. is given by α j m V q αjm = j m j1mq α j V αj Here α represents all the (other) quantum numbers of the state. including collision broadening. Computation of the atomic matrix element is usually done in the Electric Dipole approximation (See section 28. In the case of a simple spatial operator like r. the decay rate formula becomes Γtot =
3 αωin 2πc2
dΩγ ˆ · φn rφi 2 . and atomic recoil.46 With this phase space integral done aided by the delta function. Γtot = 2π¯ 2 m2 c3 λ h This decay rate still contains the integral over photon directions and a sum over ﬁnal state polarization. the general formula for the decay rate is e2 (Ei − En ) dΩγ  φn e−ik·r ˆ(λ) · pe φi 2 . not the angular momentum quantum numbers. The distribution in frequency follows a BreitWigner distribution. Ii (ω) = φi (ω)2 = 1 (ω − ω0 )2 +
Γ2 4
In addition to the inherent energy width of a state.
λ
The atomic matrix element of the vector operator r is zero unless certain constraints on the angular momentum of initial and ﬁnal states are satisﬁed. The Full Width at Half Maximum (FWHM) of the energy distribution of a state is h ¯ Γtot .
3 √ 2αωin = (2)(4π) 4 6 2 3c 5 2 3 4αωin √ 1 4 6 = 2 12π 9c 5 2
Γ2p→1s
2 3
a0
2 3
a0
We derive a simple result for the total decay rate of a state.5) e−ik·r ≈ 1 which is valid if the wavelength of the photon is much larger than the size of the atom. for example the 2p decay rate. Doppler broadening. Γ2p→1s =
3 4αωin √ 4 6 2 9c
2 3
5
2
a0
The total decay rate is related to the energy width of an excited state. 3 4αωin rni 2 Γtot = 3c2 This can be used to easily compute decay rates for Hydrogen. With the help of some commutation relations. The selection rules for electric dipole (E1) transitions are: Δ = ±1 Δm = 0. only the orbital angular momentum is involved.
y.
. z. A massive scalar ﬁeld falls oﬀ exponentially r and the larger the mass.
0. The EulerLagrange equation gives ∂ ∂ φ − μ2 φ = ρ ∂xμ ∂xμ which is the known as the KleinGordon equation with a source and is a reasonable relativistic equation for a scalar ﬁeld. LASERs. Using Fourier transforms. (See section 19) it is most convenient to make a small modiﬁcation to the system of units that are used. the faster the fall oﬀ.
0.38
The Classical Electromagnetic Field
For the study of the Maxwell ﬁeld. In Rationalized HeavisideLorentz Units the ﬁelds are √ all reduced by a factor of 4π and the charges are increased by the same factor. x3 . the o scattering of light. and xray absorption. x2 . including photon angular distributions. φ(x) = −Ge−μr 4πr
This is a ﬁeld that falls oﬀ much faster than 1 . A Lorentz scalar Lagrangian density will be derived for each ﬁeld theory we construct.47 The quantum theory of EM radiation can be used to understand many phenomena.37
Classical Field Theory
A review of classical ﬁeld theory (See section 30) is useful to ground our development of relativistic quantum ﬁeld theories for photons and electrons. It would have simpliﬁed many things if Maxwell had started oﬀ with this set of units. x4 ) = (x. From the Lagrangian we can derive a ﬁeld equation called the EulerLagrange equation. as well as the Lagrangians we use. the ﬁeld from a point source can be computed. We will work with 4vectors like the coordinate vector below (x1 . ∂ ∂xμ ∂L ∂(∂φ/∂xμ ) − ∂L =0 ∂φ
The Lagrangian for a massive scalar ﬁeld φ can be deduced from the requirement that it be a scalar L=− 1 2 ∂φ ∂φ + μ2 φ2 ∂xν ∂xν + φρ
where the last term is the interaction with a source. With this change Maxwell’s equations. the M¨ssbauer eﬀect. photon polarization. ict) using the i to get a − in the time term in a dot product (instead of using a metric tensor). This ﬁts the form of the force between nucleons fairly well although the actual nuclear force needs a much more detailed study. the photoelectric eﬀect. are simpliﬁed.
With the ﬁelds so derived from the vector potential. (which is a Lorentz vector). ∂xν This is called the Lorentz condition. Since E&M is a well understood theory. 1 1 L = − Fμν Fμν + jμ Aμ 4 c Note that (apart from the speed of light not being set to 1) the Lagrangian does not contain needless constants in this set of units. there is still substantial gauge freedom possible. The last term is a source term which provides the interaction between the EM ﬁeld and charged particles. ∂Fμν jμ = ∂xν c We now wish to pick a scalar Lagrangian. iφ) ∂Aν ∂Aμ = − ∂xμ ∂xν
Note that Fμν is automatically antisymmetric under the interchange of the indices. Even with this satisﬁed. the Lagrangian that is known to give the right equations is also known. In working with this Lagrangian. we will treat each component of A as an independent ﬁeld. Gauge transformations can be made as shown below. two of Maxwell’s equations are automatically satisﬁed. ⎛ ⎞ 0 Bz −By −iEx 0 Bx −iEy ⎟ ⎜ −Bz Fμν = ⎝ ⎠ By −Bx 0 −iEz iEx iEy iEz 0 This ﬁeld tensor can simply be written in terms of the vector potential. In this case.48 As is well known from classical electricity and magnetism. The free ﬁeld Hamiltonian density can be computed according to the standard prescription yielding ∂L ∂(∂Aμ /∂x4 ) H = Fμ4 = (Fμ4 ) = if there are no source terms in the region. ∂Aν = 0. Gauge symmetry may be used to put a condition on the vector potential. the EulerLagrange equation is Maxwell’s equation as written above. Aμ → Aμ + ∂Λ ∂xμ 2Λ = 0 ∂Aμ −L ∂x4
1 2 (E + B 2 ) 2
. the electric and magnetic ﬁeld components are actually elements of a rank 2 Lorentz tensor. The remaining two equations can be written as one 4vector equation. Aμ Fμν = (A.
α ) 2¯ ω h 1 a† ak.α + c∗ ) k. a† .α (t)c∗ (t) + c∗ (t)ck. The canonical coordinate and momenta may be found Qk.α ] = [Qk. ˆ(2) .α − iPk. Pk .α .α c for the harmonic oscillator at each frequency.α + iPk. [Qk.α .α 2 δkk δαα
. we can compute the Hamiltonian (density integrated over volume). t) = √ V
2
ˆ(α) ck.α ) 2¯ ω h 1 √ (ωQk.α − c∗ ) k.α (t)eik·x + c∗ (t)e−ik·x k. In calculating the Hamiltonian. We assume that a coordinate and its conjugate momentum have the same commutator as in wave mechanics and that coordinates from diﬀerent oscillators commute.α c
iω (ck. we write the Hamiltonian in terms of raising and lowering operators that have the same commutation relations as in the 1D harmonic oscillator. care has been taken not to commute the Fourier coeﬃcients and their conjugates.α = Pk. the two polarization vectors must be picked so that ˆ(1) .α + h ¯ω k. H =
k.49
0.α a† k. We decompose the radiation ﬁeld into its Fourier components 1 A(x.α k.α
This Hamiltonian will be used to quantize the EM ﬁeld.α ] = i¯ δkk δαα h 0 0
As was done for the 1D harmonic oscillator. and k form a right handed orthogonal system.α ] = [Pk.α (t) k. Pk .α H ak.α k = = = = 1 √ (ωQk. Plugging the Fourier decomposition into the formula for the Hamiltonian density and using the transverse nature of the radiation ﬁeld. Once the wave vector is chosen.39
Quantization of the EM Field
The Hamiltonian for the Maxwell ﬁeld may be used to quantize the ﬁeld (See section 32) in much the same way that one dimensional wave mechanics was quantized.α . and ck.α . The radiation ﬁeld can be shown to be the transverse part of the ﬁeld A⊥ while static charges give rise to A and A0 . Qk .α = − 1 (ck. ak.α
k α=1
where ˆ(α) are real unit vectors.α is the coeﬃcient of the wave with wave vector k and polarization vector ˆ(α) .α
ω c
2
ck.
The states can be labeled by a quantum number nk. e¯ h (k × ˆ(λ) ) · σ 2mc
.α2 .α k.α .α + k.α + 1 2 h ¯ω
The Fourier coeﬃcients can now be written in terms of the raising and lowering operators for the ﬁeld.α (t)eik·x + a† (t)e−ik·x k..α a† 0 k.α Aμ = = = h ¯ c2 ak. a† a† .α
1 2
States of the ﬁeld are given by the occupation number of each possible photon state..50 This means everything we know about the raising and lowering operators applies here. .α h ¯ c2 1 √ 2ω V kα 1 2
(α) μ
ak.α 1 2 h ¯ω = Nk. nk1 .α +
k.α a† + a† ak.α = = a† ak. Aμ = 1 √ V h ¯ c2 2ω
(α) μ
ak.α 0 = a† . the next term in the expansion of eik·x is ik · x. .. Energies are in steps of ¯ ω and there must be a ground state.αi )nki . We can now write the quantized radiation ﬁeld in terms of the operators at t = 0. This term gets split according to its rotation and Lorentz transformation properties into the Electric Quadrupole term and the Magnetic Dipole term.α k.α
kα
Beyond the Electric Dipole approximation.. ck.α (0)eikρ xρ + a† (0)e−ikρ xρ k. Any state with multiple photons will automatically be symmetric under the interchange of pairs of photons because the operators commute. The interaction of the electron spin with the magnetic ﬁeld is of the same order and should be included together with the E2 and M1 terms.αi !
0
Any state can be constructed by operating with creation operators on the vacuum state.α k k k.1).α
h ¯ ω Nk.αi . nk2 . =
i
(a† i .α 2ω h ¯ c2 † a 2ω k..α
H
= =
h ¯ ω ak.α
k.α a† ak.αi k nki .α This is essentially the same result as our earlier guess to put an n + 1 in the emission operator (See Section 28.α c∗ k.α1 .α k. h H Nk. nki .
once to annihilate the initial state photon and once to create the ﬁnal state photon. k ˆ(α ) A · Ai. or the A · p term in second order can contribute to scattering. The matrix element of the A2 term to go from a photon of wave vector k and an atomic state i to a scattered photon of wave vector k and an atomic state n is particularly simple since it contains no atomic coordinates or momenta. By balancing the reaction rates proportional to N and N + 1 for absorption and emission in equilibrium the energy density in the radiation ﬁeld inside a cavity is easily derived. The quantized ﬁeld is very helpful in the derivation of Planck’s black body radiation formula that started the quantum revolution. or 1 unit.α
either the A term in ﬁrst order. The three terms come from the three Feynman diagrams that contribute to the scattering to order e2 . Since it is an (axial) vector operator.51 The Electric Quadrupole (E2) term does not change parity and gives us the selection rule. Since the quantized ﬁeld contains both creation and annihilation operators. U (ν) = U (ω) 8π hν 3 dω = 3 hω/kT dν c e¯ −1
0. kˆ(α) 2mc2 = h e 2 1 ¯ c2 √ 2mc2 V ω ω
(α) (α ) −i(ω−ω )t δni μ μ e
The second order terms can change atomic states because of the p operator. Both of these amplitudes are of order e2 . 1 Aμ (x) = √ V
2
kα
h ¯ c2 2ω
(α) μ
ak. it changes angular momentum by 0. dσelas = dΩ e2 4πmc2
2 2
mω h ¯
2
ωji
j
iˆ · xj jˆ · xi iˆ · xj jˆ · xi − ωji − ω ωji + ω
. with the help of some commutators. +1. The cross section for photon scattering is then given by the dσ = dΩ e2 4πmc2
2 2
ω ω
1 δni ˆ · ˆ − m¯ h
j
nˆ · pj jˆ · pi nˆ · pj jˆ · pi + ωji − ω ωji + ω
KramersHeisenberg Formula. e2 n.40
Scattering of Photons
(See section 33) The quantized photon ﬁeld can be used to compute the cross section for photon scattering. To scatter a photon the ﬁeld must act twice. 
n
− i ≤ 2 ≤
n
+
i
The Magnetic Dipole term (M1) does not change parity but may change the spin. This result can be specialized for the case of elastic scattering.α (0)eikρ xρ + a† (0)e−ikρ xρ k. The electric dipole approximation is used to simplify the atomic matrix element at low energy where the wavelength is long compared to atomic size.
the result is inﬁnite.52 Lord Rayleigh calculated low energy elastic scattering of light from atoms using classical electromagnetism. The quantum self energy correction (See section 34) is also inﬁnite although it can be rendered ﬁnite if we accept the fact that out theories are not valid up to inﬁnite energies. keeping resonant scattering cross sections from going to inﬁnity. complex.41
Electron Self Energy
Even in classical electromagnetism. h −Γn t ψn (x. ω >> 1 eV. dσ = dΩ e2 4πmc2
2
ˆ · ˆ 
2
The scattering is roughly energy independent and the only angular dependence is on polarization. then the cross section approaches that for scattering from a free electron. It is the diﬀerence between the bound electron’s self energy and that for a free electron in which we are interested. t) = ψn (x)e−i(En + (ΔEn ))t/¯ e 2 This gives us the exponential decay behavior that we expect. The quantum self energy correction has important. Thomson Scattering. ΔEn =
k. if one can calculates the energy needed to assemble an electron. Scattered light can be polarized even if incident light is not. 2 (ΔEn ) = Γn − h ¯ The time dependence of the wavefunction for the state ψn is modiﬁed by the self energy correction. If the energy of the scattered photon is much bigger than the binding energy of the atom. It causes observable energy shifts in Hydrogen and it helps us solve the problem of inﬁnities due to energy denominators from intermediate states. ΔEf ree = − 2αEcut−of f 2 p 3πm2 c2
. so that blue light scatters more than red light does in the colorless gasses in our atmosphere. measurable eﬀects.α j
Hnj 2
1 − ei(ωnj −ω)t h ¯ (ωnj − ω)
The result is. The imaginary part of the self energy correction is directly related to the width of the state. The real part of the correction should be studied to understand relative energy shifts of states. The coupled diﬀerential equations from ﬁrst order perturbation theory for the state under study φn and intermediate states ψj may be solved for the self energy correction. yet electrons exist. The self energy correction for a free particle can be computed. in general.
0. If the energy of the scattered photon is less than the energy needed to excite the atom. then the cross section is proportional to ω 4 .
One can incorporate spin into the nonrelativistic equation by using the Schr¨dingerPauli Hamiltonian o which contains the dot product of the Pauli matrices with the momentum operator. The result can be well accounted for by the self energy correction. H= e 1 e¯ h [p + A(r. t) 2m c 2mc
This Hamiltonian acts on a two component spinor.3%. For the nonrelativistic deﬁnition of the energy of a free electron. We can extend this concept to use the relativistic energy equation. t)]2 − eφ(r. Since the observed mass of the electron already accounts for most of the self energy correction for a bound state. the correction to the mass is only about 0.42
The Dirac Equation
Our goal is to ﬁnd the analog of the Schr¨dinger equation for relativistic spin onehalf particles (See o section 35). we should note that even in the Schr¨dinger equation. Retherford used microwave techniques to determine the splitting 1 1 between the 2S 2 and 2P 2 states in Hydrogen. t)] 2m c
2
− eφ(r. t)
A little computation shows that this gives the correct interaction with spin.53 We automatically account for this correction by a change in the observed mass of the electron. H= e 1 σ · [p + A(r. the interaction of the o ﬁeld with spin was rather ad hoc. The idea is to replace p with σ · p in the relativistic energy equation. The self energy correction for a bound state then is. Lamb and R.
(obs) ΔEn
=
ΔEn +
2αEcut−of f np2 n 3πm2 c2
In 1947. E − p2 = (mc)2 c E + σ · p = (mc)2 c
2
E −σ·p c ∂ ∂ + i¯ σ · ∇ h i¯ h − i¯ σ · ∇ φ = (mc)2 φ h i¯ h ∂x0 ∂x0
.
(obs) ΔEn =
4α5 3πn3
log
mc2 2¯ ωnj h¯
+
11 1 − 24 5
mc2
0. an increase in the mass decreases the energy. mobs = (1 + 4αEcut−of f )mbare 3πmc2
If we cut oﬀ the integral at me c2 . C. There was no explanation of the gyromagnetic ratio of 2. Willis E. t) + σ · B(r. Our nonrelativistic calculation gives a qualitative explanation of the eﬀect. however. at least when relativistic quantum mechanics is used. we must correct for this eﬀect to avoid double counting of the correction.
54 Instead of an equation which is second order in the time derivative, we can make a ﬁrst order equation, like the Schr¨dinger equation, by extending this equation to four components. o φ(L) φ(R) = = φ 1 mc
i¯ h
∂ − i¯ σ · ∇ φ(L) h ∂x0
Now rewriting in terms of ψA = φ(R) + φ(L) and ψB = φ(R) − φ(L) and ordering it as a matrix equation, we get an equation that can be written as a dot product between 4vectors. −i¯ ∂x0 h ∂ −i¯ σ · ∇ h i¯ ∂x0 h ∂ = = h ¯ h ¯ 0 −iσ · ∇ iσ · ∇ 0 0 iσi −iσi 0 + 1 0
∂ ∂x4
0
∂ − ∂x4
i¯ σ · ∇ h
0 0 −1
∂ + ∂xi
∂ ∂ = h γμ ¯ ∂x4 ∂xμ
Deﬁne the 4 by 4 matrices γμ are by. γi γ4 = = 0 iσi 1 0 −iσi 0 0 −1
With this deﬁnition, the relativistic equation can be simpliﬁed a great deal γμ ∂ mc + ∂xμ h ¯ ψ=0
where the gamma matrices are given by 0 ⎜0 γ1 = ⎝ 0 ⎛i 0 ⎜0 γ3 = ⎝ i 0 ⎛ 0 0 i 0 0 0 0 −i 0 −i 0 0 −i 0 0 0 ⎞ −i 0 ⎟ ⎠ 0 0 ⎞ 0 i⎟ ⎠ 0 0 ⎞ 0 0 0 −1 ⎜ 0 0 1 0 ⎟ γ2 = ⎝ ⎠ 0 1 0 0 ⎛ −1 0 0 0 ⎞ and they satisfy anticommutation relations. 1 0 0 0 0 ⎟ ⎜0 1 0 γ4 = ⎝ ⎠ 0 0 −1 0 0 0 0 −1 {γμ , γν } = 2δμν In fact any set of matrices that satisfy the anticommutation relations would yield equivalent physics results, however, we will work in the above explicit representation of the gamma matrices. ¯ Deﬁning ψ = ψ † γ4 , ¯ jμ = icψγμ ψ satisﬁes the equation of a conserved 4vector current ∂ jμ = 0 ∂xμ ⎛
55 and also transforms like a 4vector. The fourth component of the vector shows that the probability density is ψ † ψ. This indicates that the normalization of the state includes all four components of the Dirac spinors. For nonrelativistic electrons, the ﬁrst two components of the Dirac spinor are large while the last two are small. ψA ψB c e pc ψB ≈ σ · p + A ψA ≈ ψA 2mc2 c 2mc2 ψ= We use this fact to write an approximate twocomponent equation derived from the Dirac equation in the nonrelativistic limit. Ze2 p4 h p2 Ze2 L · S Ze2 ¯ 2 3 − − + + δ (r) ψ 2m 4πr 8m3 c2 8πm2 c2 r3 8m2 c2 = E (N R) ψ
This “Schr¨dinger equation”, derived from the Dirac equation, agrees well with the one we o used to understand the ﬁne structure of Hydrogen. The ﬁrst two terms are the kinetic and potential energy terms for the unperturbed Hydrogen Hamiltonian. The third term is the relativistic correction to the kinetic energy. The fourth term is the correct spinorbit interaction, including the Thomas Precession eﬀect that we did not take the time to understand when we did the NR ﬁne structure. The ﬁfth term is the so called Darwin term which we said would come from the Dirac equation; and now it has. For a free particle, each component of the Dirac spinor satisﬁes the KleinGordon equation.
h ψp = up ei(p·x−Et)/¯
This is consistent with the relativistic energy relation. The four normalized solutions for a Dirac particle at rest are. 1 √ V ⎛ ⎞ 1 ⎜ 0 ⎟ −imc2 t/¯ h ⎝ ⎠e 0 0 ⎛ ⎞ 0 ⎜ 1 ⎟ −imc2 t/¯ h ⎝ ⎠e 0 0 ⎛ ⎞ 0 ⎜ 0 ⎟ +imc2 t/¯ h ⎝ ⎠e 1 0 ⎛ ⎞ 0 ⎜ 0 ⎟ +imc2 t/¯ h ⎝ ⎠e 0 1
ψ (1) = ψE=+mc2 ,+¯ /2 h
=
ψ (2) = ψE=+mc2 ,−¯ /2 h
=
1 √ V
ψ (3) = ψE=−mc2 ,+¯ /2 h
=
1 √ V
ψ (4) = ψE=−mc2 ,−¯ /2 h
=
1 √ V
56 The ﬁrst and third have spin up while the second and fourth have spin down. The ﬁrst and second are positive energy solutions while the third and fourth are “negative energy solutions”, which we still need to understand. The next step is to ﬁnd the solutions with deﬁnite momentum. The four plane wave solutions to the Dirac equation are ψp ≡ where the four spinors are given by. ⎛ up =
(1) (r)
mc2 (r) i(p·x−Et)/¯ h u e EV p ⎞ ⎟ ⎟ ⎠ up =
(2)
E + mc2 ⎜ ⎜ 2mc2 ⎝ ⎛
1 0
⎛
(3) up
=
−E + mc2 ⎜ ⎜ 2mc2 ⎝
pz c E+mc2 (px +ipy )c E+mc2 ⎞ −pz c −E+mc2 −(px +ipy )c ⎟ −E+mc2 ⎟
⎟ E + mc2 ⎜ ⎜ (px −ipy )c ⎟ ⎝ E+mc2 ⎠ 2 2mc
−pz c E+mc ⎛ −(px −ipy )c ⎞
2
0 1
⎞
1 0
⎠
(4) up
=
−E + mc2 ⎜ ⎜ 2mc2 ⎝
−E+mc2 pz c −E+mc2
0 1
⎟ ⎟ ⎠
E is positive for solutions 1 and 2 and negative for solutions 3 and 4. The spinors are orthogonal up
(r)†
up
(r )
=
E δrr mc2
and the normalization constants have been set so that the states are properly normalized and the spinors follow the convention given above, with the normalization proportional to energy. The solutions are not in general eigenstates of any component of spin but are eigenstates of helicity, the component of spin along the direction of the momentum.
h Note that with E negative, the exponential ei(p·x−Et)/¯ has the phase velocity, the group velocity and the probability ﬂux all in the opposite direction of the momentum as we have deﬁned it. This clearly doesn’t make sense. Solutions 3 and 4 need to be understood in a way for which the nonrelativistic operators have not prepared us. Let us simply relabel solutions 3 and 4 such that
p → −p E → −E
so that all the energies are positive and the momenta point in the direction of the velocities. This means we change the signs in solutions 3 and 4 as follows. ⎛ ⎞ 1 ⎟ 0 E + mc2 ⎜ (1) h ⎜ pz c ⎟ ei(p·x−Et)/¯ ψp = ⎝ E+mc2 ⎠ 2EV ⎛ ψp
(2) (px +ipy )c E+mc2
=
⎟ E + mc2 ⎜ h ⎜ (px −ipy )c ⎟ ei(p·x−Et)/¯ ⎝ E+mc2 ⎠ 2EV
−pz c E+mc2
0 1
⎞
57 ⎛ ψp
(3) pz c E+mc2 (px +ipy )c E+mc2
⎞ ⎟ −i(p·x−Et)/¯ h ⎟e ⎠
=
E + mc2 ⎜ ⎜ 2EV ⎝
⎛ (px −ipy )c ⎞
(4) ψp
1 0
=
E + mc2 ⎜ ⎜ 2EV ⎝
E+mc2 −pz c E+mc2
0 1
⎟ −i(p·x−Et)/¯ h ⎟e ⎠
We have plane waves of the form
h e±ipμ xμ /¯
with the plus sign for solutions 1 and 2 and the minus sign for solutions 3 and 4. These ± sign in the exponential is not very surprising from the point of view of possible solutions to a diﬀerential equation. The problem now is that for solutions 3 and 4 the momentum and energy operators must have a minus sign added to them and the phase of the wave function at a ﬁxed position behaves in the opposite way as a function of time than what we expect and from solutions 1 and 2. It is as if solutions 3 and 4 are moving backward in time. If we change the charge on the electron from −e to +e and change the sign of the exponent, the Dirac equation remains the invariant. Thus, we can turn the negative exponent solution (going backward in time) into the conventional positive exponent solution if we change the charge to +e. We can interpret solutions 3 and 4 as positrons. We will make this switch more carefully when we study the charge conjugation operator. The Dirac equation should be invariant under Lorentz boosts and under rotations, both of which are just ∂ changes in the deﬁnition of an inertial coordinate system. Under Lorentz boosts, ∂xμ transforms like a 4vector but the γμ matrices are constant. The Dirac equation is shown to be invariant under boosts along the xi direction if we transform the Dirac spinor according to ψ Sboost = = Sboost ψ χ χ cosh + iγi γ4 sinh 2 2
with tanh χ = β. The Dirac equation is invariant under rotations about the k axis if we transform the Dirac spinor according to ψ Srot with ijk is a cyclic permutation. Another symmetry related to the choice of coordinate system is parity. Under a parity inversion operation the Dirac equation remains invariant if ψ = SP ψ = γ4 ψ = Srot ψ θ θ = cos + γi γj sin 2 2
58 ⎞ 1 0 0 0 0 ⎟ ⎜0 1 0 Since γ4 = ⎝ ⎠, the third and fourth components of the spinor change sign while the 0 0 −1 0 0 0 0 −1 ﬁrst two don’t. Since we could have chosen −γ4 , all we know is that components 3 and 4 have the opposite parity of components 1 and 2. From 4 by 4 matrices, we may derive 16 independent components of covariant objects. We deﬁne the product of all gamma matrices. γ5 = γ1 γ2 γ3 γ4 which obviously anticommutes with all the gamma matrices. {γμ , γ5 } = 0 For rotations and boosts, γ5 commutes with S since it commutes with the pair of gamma matrices. For a parity inversion, it anticommutes with SP = γ4 . The simplest set of covariants we can make from Dirac spinors and γ matrices are tabulated below. Classiﬁcation Scalar Pseudoscalar Vector Axial Vector Rank 2 antisymmetric tensor Total Covariant Form ¯ ψψ ¯ 5ψ ψγ ¯ ψγμ ψ ¯ 5 γμ ψ ψγ ¯ ψσμν ψ no. of Components 1 1 4 4 6 16 ⎛
Products of more γ matrices turn out to repeat the same quantities because the square of any γ matrix is 1. For many purposes, it is useful to write the Dirac equation in the traditional form Hψ = Eψ. To do this, we must separate the space and time derivatives, making the equation less covariant looking. γμ ∂ mc + ∂xμ h ¯ ψ=0 ∂ ψ ∂t
h icγ4 γj pj + mc2 γ4 ψ = −¯
Thus we can identify the operator below as the Hamiltonian. H = icγ4 γj pj + mc2 γ4 The Hamiltonian helps us identify constants of the motion. If an operator commutes with H, it represents a conserved quantity. Its easy to see the pk commutes with the Hamiltonian for a free particle so that momentum will be conserved. The components of orbital angular momentum do not commute with H. [H, Lz ] = icγ4 [γj pj , xpy − ypx ] = hcγ4 (γ1 py − γ2 px ) ¯
59 The components of spin also do not commute with H. [H, Sz ] = hcγ4 [γ2 px − γ1 py ] ¯ But, from the above, the components of total angular momentum do commute with H. [H, Jz ] = [H, Lz ] + [H, Sz ] = hcγ4 (γ1 py − γ2 px ) + hcγ4 [γ2 px − γ1 py ] = 0 ¯ ¯ The Dirac equation naturally conserves total angular momentum but not the orbital or spin parts of it. We can also see that the helicity, or spin along the direction of motion does commute. [H, S · p] = [H, S] · p = 0 For any calculation, we need to know the interaction term with the Electromagnetic ﬁeld. Based on the interaction of ﬁeld with a current 1 Hint = − jμ Aμ c and the current we have found for the Dirac equation, the interaction Hamiltonian is. Hint = ieγ4 γk Ak This is simpler than the nonrelativistic case, with no A2 term and only one power of e. The Dirac equation has some unexpected phenomena which we can derive. Velocity eigenvalues for electrons are always ±c along any direction. Thus the only values of velocity that we could measure are ±c. Localized states, expanded in plane waves, contain all four components of the plane wave solutions. Mixing components 1 and 2 with components 3 and 4 gives rise to Zitterbewegung, the very rapid oscillation of an electrons velocity and position.
4
vk
=
p r=1 2
cp,r 2
4
p k c2 E
+
p r=1 r =3
mc3 ∗ (r )† (r) (r)† (r ) h h c cp,r up iγ4 γk up e−2iEt/¯ cp,r c∗ up iγ4 γk up e2iEt/¯ p,r E p,r
The last sum which contains the cross terms between negative and positive energy represents extremely high frequency oscillations in the expected value of the velocity, known as Zitterbewegung. The expected value of the position has similar rapid oscillations. It is possible to solve the Dirac equation exactly for Hydrogen in a way very similar to the nonrelativistic solution. One diﬀerence is that it is clear from the beginning that the total angular momentum is a constant of the motion and is used as a basic quantum number. There is another conserved quantum number related to the component of spin along the direction of J. With these quantum numbers, the radial equation can be solved in a similar way as for the nonrelativistic case yielding the energy relation. mc2 E= Z 2 α2 1+ 2 2 nr + (j+ 1 ) −Z 2 α2 2
60 We can identify the standard principle quantum number in this case as n = nr + j + 1 . This result gives 2 the same answer as our nonrelativistic calculation to order α4 but is also correct to higher order. It is an exact solution to the quantum mechanics problem posed but does not include the eﬀects of ﬁeld theory, such as the Lamb shift and the anomalous magnetic moment of the electron. A calculation of Thomson scattering shows that even simple low energy photon scattering relies on the “negative energy” or positron states to get a nonzero answer. If the calculation is done with the two diagrams in which a photon is absorbed then emitted by an electron (and viceversa) the result is zero at low energy because the interaction Hamiltonian connects the ﬁrst and second plane wave states with the third and fourth at zero momentum. This is in contradiction to the classical and nonrelativistic calculations as well as measurement. There are additional diagrams if we consider the possibility that the photon can create and electron positron pair which annihilates with the initial electron emitting a photon (or with the initial and ﬁnal photons swapped). These two terms give the right answer. The calculation of Thomson scattering makes it clear that we cannot ignore the new “negative energy” or positron states. The Dirac equation is invariant under charge conjugation, deﬁned as changing electron states into the opposite charged positron states with the same momentum and spin (and changing the sign of external ﬁelds). To do this the Dirac spinor is transformed according to. ψ = γ2 ψ ∗ Of course a second charge conjugation operation takes the state back to the original ψ. Applying this to the plane wave solutions gives ψp = ψp = ψp = ψp =
(4) (3) (2) (1)
mc2 (1) i(p·x−Et)/¯ h u e EV p mc2 (2) i(p·x−Et)/¯ h u e EV p mc2 (3) i(p·x+Et)/¯ h u e EV p mc2 (4) i(p·x+Et)/¯ h u e EV p
→ − → → → −
(1)
mc2 (4) i(−p·x+Et)/¯ h u e ≡ EV −p mc2 (3) i(−p·x+Et)/¯ h ≡ u e EV −p mc2 (2) i(−p·x−Et)/¯ h u e EV −p mc2 (1) i(−p·x−Et)/¯ h u e EV −p
(2)
mc2 (1) i(−p·x+Et)/¯ h v e EV p mc2 (2) i(−p·x+Et)/¯ h v e EV p
which deﬁnes new positron spinors vp
and vp
that are charge conjugates of up and up .
(1)
(2)
0.43
The Dirac Equation
To proceed toward a ﬁeld theory for electrons and quantization of the Dirac ﬁeld we wish to ﬁnd a scalar ¯ Lagrangian that yields the Dirac equation. From the study of Lorentz covariants we know that ψψ is a scalar and that we can form a scalar from the dot product of two 4vectors as in the Lagrangian below. The Lagrangian cannot depend explicitly on the coordinates. ∂ ¯ ψ − mc2 ψψ L = −c¯ ψγμ h¯ ∂xμ (We could also add a tensor term but it is not needed to get the Dirac equation.) The independent ¯ ﬁelds are considered to be the 4 components of ψ and the four components of ψ. The EulerLagrange
61 ¯ ¯ equation using the ψ independent ﬁelds is simple since there is no derivative of ψ in the Lagrangian. ∂ ∂xμ ∂L ¯ ∂(∂ ψ/∂xμ ) − ∂L ¯ =0 ∂ψ ∂L ¯ =0 ∂ψ
−c¯ γμ h
∂ ψ − mc2 ψ = 0 ∂xμ ∂ mc + γμ ψ=0 ∂xμ h ¯
This gives us the Dirac equation indicating that this Lagrangian is the right one. The EulerLagrange equation derived using the ﬁelds ψ is the Dirac adjoint equation, The Hamiltonian density may be derived from the Lagrangian in the standard way and the total Hamiltonian computed by integrating over space. Note that the Hamiltonian density is the same as the Hamiltonian derived from the Dirac equation directly. H= h ψ † ¯ cγ4 γk ∂ + mc2 γ4 ψd3 x ∂xk
We may expand ψ in plane waves to understand the Hamiltonian as a sum of oscillators.
4
ψ(x, t) =
p r=1 4
mc2 (r) h cp,r up ei(p·x−Et)/¯ EV mc2 ∗ (r)† −i(p·x−Et)/¯ h c u e EV p,r p
ψ † (x, t) =
p r=1
Writing the Hamiltonian in terms of these ﬁelds, the formula can be simpliﬁed yielding
4
H
=
p r=1
E c∗ cp,r . p,r
By analogy with electromagnetism, we can replace the Fourier coeﬃcients for the Dirac plane waves by operators.
4
H
=
p r=1 4
E bp
(r)† (r) bp
ψ(x, t) =
p r=1 4
mc2 (r) (r) i(p·x−Et)/¯ h b up e EV p mc2 (r)† (r)† −i(p·x−Et)/¯ h b up e EV p
(r)†
ψ † (x, t) =
p r=1
The creation an annihilation operators bp
and bp satisfy anticommutation relations.
(r)
62
{bp , bp
(r)
(r)
(r )† (r)
}
= δrr δpp = 0 = 0 = bp
(r)† (r) bp
{bp , bp }
(r)† (r)† {bp , bp } (r) Np
Np is the occupation number operator. The anticommutation relations constrain the occupation number to be 1 or 0. The Dirac ﬁeld and Hamiltonian can now be rewritten in terms of electron and positron ﬁelds for which the energy is always positive by replacing the operator to annihilate a “negative energy state” with an operator to create a positron state with the right momentum and spin. dp dp
(1) (2)
(r)
= =
−bp bp
(4)†
(3)†
These anticommute with everything else with the exception that {dp , dp Now rewrite the ﬁelds and Hamiltonian.
2 (s) (s )†
} = δss δpp
ψ(x, t) =
p s=1 2
mc2 (s) (s) i(p·x−Et)/¯ (s)† (s) h h bp u p e + dp vp e−i(p·x−Et)/¯ EV mc2 (s)† (s)† −i(p·x−Et)/¯ (s) (s)† h h bp u p e + dp vp ei(p·x−Et)/¯ EV E bp
(s)† (s) bp
ψ † (x, t) =
p s=1 2
H
=
p s=1 2
− dp dp + dp
(s) (s)†
=
p s=1
E bp
(s)† (s) bp
(s)† (s) dp
−1
All the energies of these states are positive. There is an (inﬁnite) constant energy, similar but of opposite sign to the one for the quantized EM ﬁeld, which we must add to make the vacuum state have zero energy. Note that, had we used commuting operators (BoseEinstein) instead of anticommuting, there would have been no lowest energy ground state so this Energy subtraction would not have been possible. FermiDirac statistics are required for particles satisfying the Dirac equation. Since the operators creating fermion states anticommute, fermion states must be antisymmetric under interchange. Assume b† and br are the creation and annihilation operators for fermions and that r they anticommute. {b† , b† } = 0 r r
63 The states are then antisymmetric under interchange of pairs of fermions. b† b† 0 = −b† b† 0 r r r r Its not hard to show that the occupation number for fermion states is either zero or one. Note that the spinors satisfy the following slightly diﬀerent equations. (iγμ pμ + mc)up = 0 (−iγμ pμ + mc)vp = 0
(s) (s)
64
1
The Problems with Classical Physics
By the late nineteenth century the laws of physics were based on Mechanics and the law of Gravitation from Newton, Maxwell’s equations describing Electricity and Magnetism, and on Statistical Mechanics describing the state of large collection of matter. These laws of physics described nature very well under most conditions, however, some measurements of the late 19th and early 20th century could not be understood. The problems with classical physics led to the development of Quantum Mechanics and Special Relativity. Some of the problems leading to the development of Quantum Mechanics are listed here. • Black Body Radiation (See section 1.1): Classical physics predicted that hot objects would instantly radiate away all their heat into electromagnetic waves. The calculation, which was based on Maxwell’s equations and Statistical Mechanics, showed that the radiation rate went to inﬁnity as the EM wavelength went to zero, “The Ultraviolet Catastrophe”. Planck solved the problem by postulating that EM energy was emitted in quanta with E = hν. • The Photoelectric Eﬀect (See section 1.2): When light was used to knock electrons out of solids, the results were completely diﬀerent than expected from Maxwell’s equations. The measurements were easy to explain (for Einstein) if light is made up of particles with the energies Planck postulated. • Atoms: After Rutherford (See section 1.3) found that the positive charge in atoms was concentrated in a very tiny nucleus, classical physics predicted that the atomic electrons orbiting the nucleus would radiate their energy away and spiral into the nucleus. This clearly did not happen. The energy radiated by atoms (See section 1.4) also came out in quantized amounts in contradiction to the predictions of classical physics. The Bohr Atom (See section 1.4.1) postulated an angular momentum quantization rule, L = n¯ for n = 1, 2, 3..., that gave the right result for hydroh gen, but turned out to be wrong since the ground state of hydrogen has zero angular momentum. It took a full understanding of Quantum Mechanics to explain the atomic energy spectra. • Compton Scattering (See section 1.6.3): When light was scattered oﬀ electrons, it behaved just like a particle but changes wave length in the scattering; more evidence for the particle nature of light and Planck’s postulate. • Waves and Particles: In diﬀraction experiments,light was shown to behave like a wave while in experiments like the Photoelectric eﬀect, light behaved like a particle. More diﬃcult diﬀraction experiments showed that electrons (as well as the other particles) also behaved like a wave, yet we can only detect an integer number of electrons (or photons). Quantum Mechanics incorporates a waveparticle duality and explains all of the above phenomena. In doing so, Quantum Mechanics changes our understanding of nature in fundamental ways. While the classical laws of physics are deterministic, QM is probabilistic. We can only predict the probability that a particle will be found in some region of space. Electromagnetic waves like light are made up of particles we call photons. Einstein, based on Planck’s formula, hypothesized that the particles of light had energy proportional to their frequency. E = hν The new idea of Quantum Mechanics is that every particle’s probability (as a function of position and time) is equal to the square of a probability amplitude function and that these probability amplitudes
65 obey a wave equation. This is much like the case in electromagnetism where the energy density goes like the square of the ﬁeld and hence the photon probability density goes like the square of the ﬁeld, yet the ﬁeld is made up of waves. So probability amplitudes are like the ﬁelds we know from electromagnetism in many ways. DeBroglie assumed E = hν for photons and other particles and used Lorentz invariance (from special relativity) to derive the wavelength for particles (See section 2.4) like electrons.
λ=
h p
The rest of wave mechanics was built around these ideas, giving a complete picture that could explain the above measurements and could be tested to very high accuracy, particularly in the hydrogen atom. We will spend several chapters exploring these ideas. * See Example 1.6.3: Assume the photon is a particle with the standard deBroglie wavelength. Use kinematics to derive the wavelength of the scattered photon as a function of angle for Compton Scattering.*
Gasiorowicz Chapter 1 Rohlf Chapters 3,6 Griﬃths does not really cover this. CohenTannoudji et al. Chapter
1.1
Black Body Radiation *
A black body is one that absorbs all the EM radiation (light...) that strikes it. To stay in thermal equilibrium, it must emit radiation at the same rate as it absorbs it so a black body also radiates well. (Stoves are black.) Radiation from a hot object is familiar to us. Objects around room temperature radiate mainly in the infrared as seen the the graph below.
66
If we heat an object up to about 1500 degrees we will begin to see a dull red glow and we say the object is red hot. If we heat something up to about 5000 degrees, near the temperature of the sun’s surface, it radiates well throughout the visible spectrum and we say it is white hot.
By considering plates in thermal equilibrium it can be shown that the emissive power over the absorption coeﬃcient must be the same as a function of wavelength, even for plates of diﬀerent materials.
E1 (λ, T ) E2 (λ, T ) = A1 (λ) A2 (λ)
It there were diﬀerences, there could be a net energy ﬂow from one plate to the other, violating the equilibrium condition.
67
111111111111111111111111111 000000000000000000000000000 111111111111111111111111111 000000000000000000000000000 111111111111111111111111111 000000000000000000000000000 111111111111111111111111111 000000000000000000000000000 Object 1 at Temperature T 111111111111111111111111111 000000000000000000000000000 111111111111111111111111111 000000000000000000000000000 111111111111111111111111111 000000000000000000000000000 111111111111111111111111111 000000000000000000000000000 111111111111111111111111111 000000000000000000000000000 111111111111111111111111111 000000000000000000000000000 Object 2 at Temperature T 111111111111111111111111111 000000000000000000000000000 111111111111111111111111111 000000000000000000000000000 111111111111111111111111111 000000000000000000000000000 111111111111111111111111111 000000000000000000000000000
Black Body at Temperature T
11111111111111111111111111 00000000000000000000000000 11111111111111111111111111 00000000000000000000000000 11111111111111111111111111 00000000000000000000000000 Object 2 at Temperature T 11111111111111111111111111 00000000000000000000000000 11111111111111111111111111 00000000000000000000000000 11111111111111111111111111 00000000000000000000000000 11111111111111111111111111 00000000000000000000000000
A black body is one that absorbs all radiation incident upon it. ABB = 1 Thus, the black body Emissive power, E(ν, T ), is universal and can be derived from ﬁrst principles. A good example of a black body is a cavity with a small hole in it. Any light incident upon the hole goes into the cavity and is essentially never reﬂected out since it would have to undergo a very large number of reﬂections oﬀ walls of the cavity. If we make the walls absorptive (perhaps by painting them black), the cavity makes a perfect black body.
There is a simple relation between the energy density in a cavity, u(ν, T ), and the black body emissive power of a black body which simply comes from an analysis of how much radiation, traveling at the
68 speed of light, will ﬂow out of a hole in the cavity in one second. E(ν, T ) = c u(ν, T ) 4
The only part that takes a little thinking is the 4 in the equation above. Rayleigh and Jeans calculated (see section 1.5.1) t he energy density (in EM waves) inside a cavity and hence the emission spectrum of a black body. Their calculation was based on simple EM theory and equipartition. It not only did not agree with data; it said that all energy would be instantly radiated away in high frequency EM radiation. This was called the ultraviolet catastrophe. 8πν 2 kT c3
u(ν, T ) =
Planck found a formula that ﬁt the data well at both long and short wavelength. hν 8πν 2 c3 ehν/kT − 1
u(ν, T ) =
His formula ﬁt the data so well that he tried to ﬁnd a way to derive it. In a few months he was able to do this, by postulating that energy was emitted in quanta with E = hν. Even though there are a very large number of cavity modes at high frequency, the probability to emit such high energy quanta vanishes exponentially according to the Boltzmann distribution. Planck thus suppressed high frequency radiation in the calculation and brought it into agreement with experiment. Note that Planck’s Black Body formula is the same in the limit that hν << kT but goes to zero at large ν while the Rayleigh formula goes to inﬁnity.
69
It is interesting to note that classical EM waves would suck all the thermal energy out of matter, making the universe a very cold place for us. The ﬁgure below compares the two calculations to some data at T = 1600 degrees. (It is also surprising that the start of the Quantum revolution came from Black Body radiation.)
So the emissive power per unit area is E(ν, T ) = hν 2πν 2 c2 ehν/kT − 1
*
* See Example 1. (He got his Nobel prize for the Photoelectric eﬀect. not for Special or General Relativity. is actually correct for EM radiation.)
. R(T ) = π2 c k 4 T 4 = (5.1: What is the temperature at the solar surface? Use both the the intensity of radiation on earth and that the spectrum peaks about 500 nm to get answers.2
The Photoelectric Eﬀect
The Photoelectric Eﬀect shows that Planck’s hypothesis. used to ﬁt the Black Body data.6.6. Einstein went further and proposed.7 degrees. E = hν. in 1905.70 We can integrate this over frequency to get the total power radiated per unit area. that light was made up of particles with energy related to the frequency of the light.2: The cosmic microwave background is black body radiation with a temperature of 2.67 × 10−8 W/m2 / ◦ K4 ) T 4 60(¯ c)3 h
* See Example 1. For what frequency (and what wavelength) does the intensity peak?*
1.
Measurements were made of the maximum electron energy versus light frequency and light intensity. as seen the the ﬁgure above. Classical physics predicted that the electron energy should increase with intensity. The kinetic energy of the electrons is given by Planck’s constant times the light frequency minus a work function W which depends on the material. as the electric ﬁeld increases. This is not observed. The electron energy is independent of intensity and depends linearly on the light frequency. 1 mv 2 = hν − W 2
.71
Cathode
e Anode γ
When light strikes a polished (metal) surface electrons are ejected.
the Coulomb force continues to increase as the α approaches the nucleus.3
The Rutherford Atom *
The classical theory of atoms held that electrons were bound to a large positive charge about the size of the atom. Data from the Photoelectric eﬀect strongly supported the hypothesis that light is composed of particles (photons).
1. For a very small nucleus. His data can be explained if the positive nucleus of an atom is very small.
He found that the α particles often scattered at angles larger than 90 degrees. and backscattering is possible.72 This equation just expresses conservation of energy with hν being the photon energy and W the binding energy of electrons in the solid.5 MeV α particles should never have backscattered because they had enough energy to overcome the coulomb force from a charge distribution. Rutherford scattered charged (α) particles from atoms to see what the positive charge distribution was. his 5.
. With a approximately uniform charge distribution. essentially plowing right through the middle.
the discovery of nuclear structure.6.
. (He probably destroyed all the atoms he “saw”. The atomic size was known from several types of experiments.73
* See Example 1. with higher and higher energy particles. the energy levels can be calculated very accurately. they should radiate energy as they accelerate.*
This brought up a new problem. the discovery of quarks inside the proton. so far. This radiation is not observed and the ground states of atoms are stable. and ﬁnally the lack of discovery. the discovery of proton structure. We will also use hydrogen a great deal in this course. If electrons orbit around the atomic nucleus. Scattering of the high energy α particles allowed Rutherford to “see” inside the atom and determine that the atomic nucleus is very small. of any quark structure. For hydrogen. Hydrogen was used to test Quantum Mechanics as it developed. according to Maxwell’s equations.4: Use Electrostatics to estimate how small a gold nucleus must be to backscatter a 5. In Quantum Mechanics.5 MeV alpha particle. the discovery of a pointlike proton inside the nucleus.) The ﬁgure below shows Rutherford’s angular distribution in his scattering experiment along with several subsequent uses of the same technique. the localization of the electron around a nucleus is limited because of the wave nature of the electron. We see Rutherford’s discovery of the tiny nucleus. where there is no multibody problem to make the calculation needlessly diﬃcult.
the transitions between energy levels. we needed to use beams of particles with smaller and smaller wavelength.74
To “see” these things at smaller and smaller distances. higher energy.4
Atomic Spectra *
Hydrogen was ultimately the true test of the quantum theory. Very high accuracy measurements were made using diﬀraction gratings. and hence. and the wavelength of light produced in the transition. These were well understood in nonrelativistic QM and understood even better in the fully relativistic Quantum Field Theory. Quantum Electrodynamics. The ﬁgure below show the energy levels in Hydrogen.
1. The Lyman series covers transitions to the ground
.
Very good approximation techniques have been developed. E = 13. Absorption at discrete energies had also been observed. the energy levels of more complex atoms can be calculated. a great deal of data existed on the discrete energies at which atoms radiated. The Rydberg formula for the energies of photons emitted by Hydrogen was developed well before the QM explanation came along. Heavier atoms provide a even richer spectrum but are much more diﬃcult to calculate. With computers and good technique. The Balmer series is due to transitions to the ﬁrst excited state and is in the visible. We will understand these splitting much later in the course.75 state and is beyond the visible part of the spectrum.
. Each atom had its own unique radiation ﬁngerprint.
By the time of Planck’s E = hν.6eV 1 1 − 2 n2 n2 1
Some of the states in heavier atoms followed the same type of formula. Better experiments showed that the spectral lines were often split into a multiplet of lines. The spectrum of mercury shown below has many more lines than seen in Hydrogen.
1
The Bohr Atom *
Bohr postulated that electrons orbited the nucleus like planets orbiting the sun.
1. we mainly see the Balmer series. He managed to ﬁt the data for Hydrogen by postulating that electrons orbited the nucleus in circular orbits. and
. with a line from PaschenBach. Molecules have many other types of excitations and can produce many frequencies of light.4.76
The ﬁgure below shows the visible part of the spectrum for several atomic or molecular sources. For Hydrogen. The spectra of diﬀerent atoms are quite distinct.
v= Plug into force equation to get formula for r. E E E E E
α2 mc2 2
= = = = =
1 mv 2 + V (r) 2 2 n¯ h α¯ c h 1 m − 2 mr r αn¯ c h 1 h α2 ¯ mc2 m − 2¯ 2 n h n2 ¯ h 2 2 2 αc α mc 1 m − 2 n n2 1 α2 mc2 α2 mc2 α2 mc2 =− − 2 n2 n2 2n2
2
The constant trum.5. 3. ¯ V (r) = −α¯ c h r αmc 1 1 = r h ¯ n2
We now compute the energy levels. for n = 1. We write the Hydrogen potential in terms of 1 e2 1 the ﬁne structure constant (See section 1..77 that angular momentum is quantized such that L = n¯ ..
=
511000 2(137)2
= 13.2): αSI = 4π 0 hc ≈ 137 . mv 2 1 e2 = r 4π 0 r2
Angular momentum quantization assumption. This is natural since h h ¯ has units of angular momentum.6 eV. Balance of forces for circular orbits. 2. Bohr’s formula gives the right Hydrogen energy spec
. h mn2 ¯ 2 r2 m2 r 2 r n2 ¯ 2 h mr 1 r = = = e2 4π 0 e2 4π 0 me2 1 4π 0 ¯ 2 n2 h n¯ h mr
Now we just want to plug v and r into the energy formula.. L = mvr = n¯ h Solve for velocity. Bohr correctly postdicted the Hydrogen energies and the size of the atom.
5
1. Bohr ﬁt the data.1
Derivations and Computations
Black Body Radiation Formulas *
(Not yet available. 1 r r = = αmc2 h ¯c (137)(1973) = 0. Although angular momentum is quantized in units of ¯ . the ground state of Hydrogen has zero h angular momentum.5. with some element of truth.2
The Fine Structure Constant and the Coulomb Potential
We will now grapple for the ﬁrst time with the problem of which set of units to use. The name for this number.
1. Advanced texts typically use CGS units in which the potential energy is V (r) = while the Standard International units V (r) = 1 −e2 4π 0 r −e2 r
We can circumvent the problem by deﬁning the dimensionless ﬁne structure constant α. the Bohr radius.53˚ A 511000
This is also about the right radius. αSI αCGS = = 1 1 e2 ≈ 4π 0 ¯ c h 137 1 e2 ≈ h ¯c 137
So in either set of units the Hydrogen potential is V (r) = −α¯ c h r
. but his model is WRONG. persists to this day despite the fact that Bohr’s assumption is wrong.78 We can also compute the ground state radius of the Bohr orbit. This would put Bohr’s electron in the nucleus.)
1.5.
5ν 4 ehν/kT − 1 5 ehν/kT −1 − ν 5 (h/kT )ehν/kT =0 (ehν/kT − 1)2 = ν(h/kT )ehν/kT (ehν/kT − 1)2
5(ehν/kT − 1) = hν/kT ehν/kT 5(1 − e−hν/kT ) = hν/kT
. (rsun = 7 × 108 m.5 × 1011 m) • and the solar spectrum which peaks at about 500 nm.67 × 10−8 = 5800 ◦ K =
Lets assume that E(λ. T ) peaks at 500 nm as one of the graphs shows.79
1. First we compute the power radiated per unit area on the solar surface.4 kilowatts per square meter.67 × 10−8 W/m2 / ◦ K4 ) T 4 and get T4 T 6. Remember f (ν)dν = g(λ)dλ for distribution functions. dsun = 1. T ). E(ν. T ) = E(λ. T ) = = 2πν 2 hν 2 ehν/kT − 1 c hν dν 2πν 2 dλ c2 ehν/kT − 1 hν hν ν 2 2πν 2 2πν 4 = 3 hν/kT c c2 ehν/kT − 1 c e −1
This peaks when ν5 ehν/kT − 1 is maximum.6. R(T ) = (5.4 × 107 5.4 × 107 W/m2 sun
We compare this to the expectation as a function of temperature.1
Examples
The Solar Temperature *
Estimate the solar temperature using • the solar radiation intensity on the earth of 1.
2 R = (1400W/m2 )(4πd2 )/(4πrsun ) = 6. We need to transform E(ν.6
1.
2
Black Body Radiation from the Early Universe *
Find the frequency ν at which the the Emissive E(ν. He measured the wavelength of the scattered photons as a function of the scattering angle.80 Lets set y = hν/kT and solve the equation y = 5(1 − e−y ) I solved this iteratively starting at y=5 and got y = 4. with the photon scattered by an angle θ and the electron recoiling at an angle φ.7)
λ =
Similarly the peak in ν occurs when ν = 2. the photons decoupled from matter and just propagated through space. The background radiation is very uniform but we are beginning to observe nonuniformities at the 10−5 level.7) = 6 × 1010 Hz (6. (6. We observe about 2.8kT /h = (1.97 implying hν = 4.6 × 10−34 )
1. We wish to derive the formula for the wavelength of the scattered photon as a function of angle. Because the universe is expanding.4 × 10−23 )(2.97kT If we take λ = 500 nm. Most of the atoms in the universe were ionized and photons interacted often with the ions or free electrons.7 degrees. T ) is a maximum. T = That’s agrees well. From the previous problem. we can say that the peak λ occurs when hν ν = = 5kT 5kT /h ch/(5kT ) = (3 × 108 )(6. The cosmic background radiation was produced when the universe was much hotter than it is now. them ν = 6 × 1014 .6 × 10−34 ) = 1mm (5)(1.4 × 10−23 )(2. T ) is a maximum for the 2.
.3
Compton Scattering *
Compton scattered high energy photons from (essentially) free electrons in 1923.6. As the universe cooled so that neutral atoms formed. the radiation has been red shifted down to a much lower temperature.6.4 × 10−23 )
1.6 × 10−34 )(6 × 1014 ) hν = = 6 × 103 = 5700 5k (5)(1. Find the wavelength λ for which E(λ. The photons were from nuclear decay and so they were of high enough energy that it didn’t matter that the electrons were actually bound in atoms.7 degree cosmic background radiation. We see these photons today as the background radiation. The ﬁgure below shows both the initial state (a) and the ﬁnal state.
We’ll put the c back in at the end.81
We solve the problem using only conservation of energy and momentum. Continuing from the energy equation E − E + m = p 2 + m2 e squaring and calculating p2 from the components e E 2 + E 2 + m2 − 2EE + 2mE − 2mE = (E − E cos θ)2 + (E sin θ)2 + m2 and writing out the squares on the right side E 2 + E 2 + m2 − 2EE + 2mE − 2mE = E 2 + E 2 − 2EE cos θ + m2 and removing things that appear on both sides −2EE + 2mE − 2mE = −2EE cos θ and grouping m(E − E ) = (E − E ) = EE 1 1 = − E E EE (1 − cos θ) (1 − cos θ) m (1 − cos θ) m
. Conservation of energy gives E+m=E + p 2 + m2 e Our goal is to solve for E in terms of cos θ so lets make sure we eliminate the φ. Lets work in units in which c = 1 for now. Assume the photon is initially moving in the z direction with energy E and that it scatters in the yz plane so that px = 0. Conservation of momentum gives E = E cos θ + pe cos φ and E sin θ = pe sin φ.
For A the actual nuclear radius of about 5 Fermis or 5 × 10−15 meters. we need 68 MeV to plow through. we need about 680 eV to plow through the nucleus.85 × 10 R
V =
The is then the kinetic energy in eV needed for a particle of charge +e to plow right through the center of a spherical charge distribution. e
1. Now we need to integrate our way into the center.7 × 10−7 = Nm/C −12 C2 /Nm2 )R 8π(8. The α particle actually has charge +2e so we need to multiply by 2. λ −λ= hc (1 − cos θ) mc2
These calculations can be fairly frustrating if you don’t decide which variables you want to keep and which you need to eliminate from your equations. what is the maximum α particle kinetic energy for which the α can be scattered right back in the direction from which it came? To solve this.6 × 10−19 C) 1.82 Since λ = h/p = h/E in our ﬁne units. λ −λ= h (1 − cos θ). This tells us directly the kinetic energy in eV needed to plow right through the charge distribution. That’s the easy part. For a nuclear radius of 5 ˚or 5 × 10−10 meters. we need to compute the potential at the center of the charge distribution relative to the potential at inﬁnity (which we will say is zero). In this case we eliminated φ by using the energy equation and computing p2 .
.
1 The potential at the surface of the nucleus is 4π 0 Ze where Z is the number of protons in the atom and R R is the nuclear radius.
0
1 1 Ze − V = 4π 0 R 4π 0 R3
R
Zerdr 3Ze 8π 0 R
V =
1 4π 0
Ze Ze + R 2R
=
So (3)(79)(1. m
We now apply the speed of light to make the units come out to be a length. 0
1 Ze − V = 4π 0 R
R
1 r3 Ze dr 4π 0 R3 r2
The
r3 R3
gives the fraction of the nuclear charge inside a radius r.4
Rutherford’s Nuclear Size *
If the positive charge in gold atoms were uniformly distributed over a sphere or radius 5 Angstroms.6.
83 Lets compare the above SI units numbers to my suggested method of using the ﬁne structure constant... Putting in the alpha charge of 2e. U= This is easier. 6Ze2 3Zα¯ c h (3)(79)(1973) = = eV = 683 eV 8π 0 R R (137)(5)
1.7
Sample Test Problems
1. What is the maximum wavelength of electromagnetic radiation which can eject electrons from a metal having a work function of 3 eV? (3 points) Answer The minimum photon energy needed to knock out an electron is 3 eV. We just need to convert that to wavelength. E ν 2π¯ c h λ 2π¯ c h λ= 3eV = = = = hν = 3eV c λ 3eV 2π(1973eV ˚ ) A ≈ 4000˚ A 3eV
2. * Based on classical electromagnetism and statistical mechanics, Rayleigh computed the energy density inside a cavity. He found that, at a temperature T, the energy density as a function of frequency was 8πν 2 u(ν, T ) = 3 kB T. c Why is this related to black body radiation? Why was this in obvious disagreement with observation? 3. What is the maximum wavelength of electromagnetic radiation which can eject electrons from a metal having a work function of 2 eV? 4. * State simply what problem with blackbody radiation caused Planck to propose the relation E = hν for light. 5. The work function of a metal is 2 eV. Assume a beam of light of wavelength λ is incident upon a polished surface of the metal. Plot the maximum electron energy (in eV) of electrons ejected from the metal versus λ in Angstroms. Be sure to label both axes with some numerical values. 6.
84
2
Diﬀraction
Feynman Lectures, Volume III, Chapter I. Gasciorawicz does not really this. Rohlf Chapters 5 Griﬃths doesn’t cover this.
2.1
Diﬀraction from Two Slits
Water waves will exhibit a diﬀractive interference pattern in a 2 slit experiment as diagrammed below. The diagram shows the crests of the water waves at some time. Downstream from the slits, we will see constructive interference where the waves from the slits are in phase and destructive interference where they are 180 degrees out of phase, for example where a crest from one slit meets a trough from the other. The plot labeled I12 shows the interference pattern at the location of the absorber. Diﬀraction is a simple wave phenomenon.
The diﬀraction of light was a well known phenomenon by the end of the 19th century and was well explained in classical ElectroMagnetic theory since light was held to be a EM wave. The diﬀraction pattern from two narrow slits is particularly easy to understand in terms of waves. The setup is shown in the diagram below.
85
d sin θ d
laser
θ
EM waves of wavelength λ are emitted from a single lightsource, like a laser. They travel to two narrow slits, (for simplicity) equidistant from the source, and a distance d apart. Light travels from the slits to a detection screen. A diﬀraction pattern can be seen on the detection screen, like the one shown in the picture below.
The center of the diﬀraction pattern occurs at the location on the screen equidistant from each slit where the waves from the two slits are in phase (because they have traveled exactly the same distance) and the ﬁelds add, so the waves interfere constructively and there is an intensity maximum. Some distance oﬀ this center of the diﬀraction pattern, there will be destructive interference between waves from the two slits and the intensity will be zero. This will occur when the distance traveled by two waves
86 diﬀers by λ/2, so the waves are 180 degrees out of phase and the ﬁelds from the two slits cancel. We can compute this location by looking at the above diagram. We assume that the distance to the screen is much greater than d. For light detected at an angle θ, the extra distance traveled from slit 1 is just d sin θ. So the angle of the ﬁrst minimum (or null) can be found from the equation d sin θ = λ . 2 More generally we will get a maximum if the paths from the slits diﬀer by an integer number of wavelengths d sin θ = nλ and we will get a null when the paths diﬀer by a half integer number wavelengths. d sin θnull = (n+1)λ . 2 Although it is very diﬃcult because electrons are charged, 2 slit electron diﬀraction has also been observed.
So, all kinds of particles seem to diﬀract indicating there is some kind of wave involved. We will now continue with some thought experiments on diﬀraction to illustrate the physics that Quantum Mechanics needed to match. * See Example 2.6.1: Derive the location of the nodes in the diﬀraction pattern from two narrow slits a distance d apart. Now try to compute the intensity distribution.*
87
2.2
Single Slit Diﬀraction
There are many other examples of diﬀraction. The picture below shows diﬀraction from a single slit where waves from diﬀerent parts of the slit interfere with each other. To get the ﬁeld at some point on the detection screen, one should integrate over the slit. * See Example 2.6.2: Derive the location of the nodes in the diﬀraction pattern from one slit of width a. Now try to compute the intensity distribution for single slit diﬀraction.*
2.3
Diﬀraction from Crystals
Electron waves were ﬁrst demonstrated by measuring diﬀraction from crystals. Davison and Germer observed diﬀraction of electrons from a Nickel crystal in 1928. They varied the electron energy to measure the electron wavelength, agreeing well with the deBroglie expectation. First we see diﬀraction from a single crystal.
Diﬀraction oﬀ polycrystalline material gives concentric rings instead of spots.
88
Diﬀraction from crystals is a powerful tool. First we see xray diﬀraction from a single Sodium Crystal which has periodic locations of the atoms.
89
Another example of diﬀraction is shown below. Here neutrons diﬀract from a single Sodium crystal.
90
2.4
The DeBroglie Wavelength
The Lorentz transformation had been postulated for ElectroMagnetic waves before Einstein developed Special Relativity. The EM waves were entirely consistent with Relativity. For example, the phase of an EM wave at some point is the same as at the Lorentz transformed point. DeBroglie applied this Lorentz invariance requirement on the phase of matter waves to determine what the wavelength must be. Its easy for us to derive the wavelength using 4vectors. Position and time form one 4vector. xμ = (ct, x) Energy and momentum form another. pμ = (E, pc) Recall that Lorentz vectors must be transformed but Lorentz scalars are automatically invariant under transformations. For example the scalar formed by dotting the 4momentum into itself is pμ pμ = −E 2 + p2 c2 = −m2 c4 . The mass of a particle is clearly Lorentz invariant. To compute the wavelength for our matter waves, lets use the scalar pμ xμ /c = −Et + p · x
91 Its already easy to see that the phase in a wave like
h ei(p·x−Et)/¯
is Lorentz invariant. To read oﬀ the wavelength, lets pick oﬀ the part of the expression that corresponds to e2πi(x/λ−νt) . We p see that 2π = h and therefore the DeBroglie wavelength is. λ ¯
λ=
h 2π¯ h = p p
DeBroglie derived this result in 1923. We can also read oﬀ the frequency ν. E = E/h 2π¯ h This was in some sense the input to our calculation. ν= The deBroglie wavelength will be our primary physics input for the development of Quantum Mechanics. Its not that this work was the most signiﬁcant, but, this wavelength summarizes most of what happened before 1923.
2.4.1
Computing DeBroglie Wavelengths
We usually quote the energy of a particle in terms of its kinetic energy in electron Volts, eV (or Million electron Volts, MeV). The reason for this is that particles are usually accelerated to some energy by an electric ﬁeld. If I let an electron (or proton...) be accelerated through a 100 Volt potential diﬀerence, it will have a kinetic energy of 100eV. The whole problem of computing a deBroglie wavelength is to convert from kinetic energy to momentum. If you always want to be correct without any need for thinking, use the relativistically correct formula for the kinetic energy T = (mc2 )2 + p2 c2 − mc2 and solve it for pc, pc = (T + mc2 )2 − (mc2 )2 then use this handy formula to get the answer. λ= h 2π¯ c h = p pc
I remember that ¯ c = 1973 eV˚ allowing me to keep the whole calculation in eV. I also know the masses h A of the particles. me c2 = 0.51 MeV mp c2 = 938.3 MeV
92 (If T <<< mc2 , make sure the precision of your calculator suﬃcient or use the nonrelativistic method below.) If you know that the particle is superrelativistic, so that T >> mc2 , then just use pc = T and life is easy. If you know that the particle is highly nonrelativistic, T << mc2 , then you can use T = √ giving pc = 2mc2 T .
p2 2m
=
(pc)2 2mc2
So, for example, compute the wavelength of a 100 eV electron. This is nonrelativistic since 100 eV ¡¡ √ 510000 eV. So pc = 106 × 100 eV or 10000 eV. λ= 12000 2π1973 = = 1.2 ˚ A pc 10000
2.5
Wave Particle Duality (Thought Experiments)
Richard Feynman (Nobel Prize for Quantum ElectroDynamics...) presents several thought experiments in his Lectures on Physics, third volume.
For our ﬁrst thought experiment, we will consider two silt diﬀraction of light. Assume that instead of using the screen, I use a sensitive photodetector. I measure the intensity of light as a function of position near the screen and ﬁnd the same set of maxima and minima that I did using my eyes.
93
Now lets turn down the intensity of the light source. For very low intensity I ﬁnd that my detector collects one photon at a time. It never collects half a photon. (With the right detector, I could again verify that for each photon, the Photoelectric eﬀect is seen and that E = hν.) So the waves that are diﬀracting are somehow made up of photons. With a low enough intensity, I can assure that only one photon is present in the apparatus at any time. I can operate my detector and collect data over a long time, summing up the number of photons detected as a function of position. What will I get for the distribution? I get exactly the same distribution as before with maxima and minima. No matter how low the intensity, (1 particle/ minute!) we still see diﬀraction. We never detect a fraction of an electron or a photon, only integer numbers.
How does a single photon interfere with itself? It must somehow travel through both slits.
Lets turn to electron diﬀraction for a minute. In our thought experiment we again have two slits.
94
We use our detector to measure the diﬀraction pattern similar to the one for photons labeled P12 below. We put a bright light source near the slits and detect light bouncing oﬀ the electron so we can see which slit it passes through.
Now we will try to see which slit each electron passes through. If we cover up slit 2 we get the distribution labeled P1 and if we /emphtextcover up slit 1 we get the intensity distribution labeled P2 .
. We could have done the same with our photons above.
In this case. If we turn the light oﬀ. Our observation of the electron as it passes through the slit has changed the resulting intensity distribution. we go back to measuring P12 . Indeed.
.95
What distribution do we see now? Actually we will see P1 + P2 if we can tell which slit the electron went through.
Can you explain why the light causes the diﬀraction pattern to disappear? Is it the mere observation? Does the light change the phase of the electron?
There are many examples of an observer changing the result of a Quantum experiment. we will do a two slit diﬀraction experiment with bullets. all we had to do is turn on the light. it is held that when a state is observed.
Finally. We must make slits big enough for the bullets to pass through. We didn’t have to look. its wave function collapses into the state “seen”.
2
Intensity Distribution for Single Slit Diﬀraction *
Derive the location of the nodes in the diﬀraction pattern from one slit of width a. High momentum implies a small deBroglie wavelength.1
Examples
Intensity Distribution for Two Slit Diﬀraction *
Derive the location of the nodes in the diﬀraction pattern from two narrow slits a distance d apart. So to see diﬀraction. Vol. Feynman Lectures on Physics.6. They always give the P1 + P2 pattern (probably diﬀerent for the bullets). Bullets are macroscopic objects with huge momenta compared to individual particles. the wavelength is tiny compared to any slit a bullet would ﬁt through.96
No matter what distance between the slits we choose.
. Why didn’t we see diﬀraction for the bullets. Now try to compute the intensity distribution. Now try to compute the intensity distribution for single slit diﬀraction.6. Can you explain this? The bullet’s wavelength is much much smaller than the actual size of the bullet. we must make the distance between the slits much smaller than we did for the photons (perhaps 1020 times smaller). But bullets are also big. This is an in lab exercise. This is an in lab exercise. Therefore no bullet diﬀraction is possible. III Chapter 1
2. For bullets.6
2. we never observe diﬀraction for the bullets.
2. They only ﬁt through big slits which must them be further apart than the slits used for photons.
What K.511 × 106 eV )(13. What is the DeBroglie wavelength for each of the following particles? The energies given are the kinetic energies.97
2. 7. What is the DeBroglie wavelength for each of the following particles? The energies given are the kinetic energies. Qualitatively plot the new electron intensity distribution from each slit and from the 2 slits combined. λ= 2π¯ c h 2π(197. p2 2m p 2 c2 2mc2 pc λ = 13.511M eV so this is nonrelativistic. The observed electron intensity distribution is plotted in the ﬁgure. A 2 slit electron diﬀraction experiment is set up as (not) shown below.6 eV )
2π¯ c h 2mc2 (13.
. What is the condition on the wavelength of the light for this eﬀect to occur? 4. it can be ”seen” which slit each electron goes through.3) M eV F ) = ≈ 120 F pc 10 M eV
2.6) ≈ 3.6 eV is much less than mc2 = 0. a) a 1 eV electron b) a 104 MeV proton 5.6 = 13.6 = = = 2mc2 (13. What is the deBroglie wavelength of an electron with 13. Now an intense light source is introduced near the two slits. must a Hydrogen atom have so that its DeBroglie wavelength is smaller than the size of the atom? (Factors of 2 are not important.33 ˚ A
10 MeV is much bigger than mc2 for an electron so it is superrelativistic and we can use E = pc. (b) An electron with 10 MeV kinetic energy. and (c) a 1 gram lead ball moving with a velocity of 10 cm/sec (one erg is one gram cm2 /sec2 ). a) a 10 eV electron b) a 1 MeV electron c) a 10 MeV proton 3.E.7
Sample Test Problems
1.) 6. Calculate the DeBroglie wavelength for (a) a proton with 10 MeV kinetic energy.6 eV of kinetic energy? What is the deBroglie wavelength of an electron with 10 MeV of kinetic energy? Answer 13. Be sure to take account of relativity where needed.6) 2π¯ h 2π¯ c h h = = = p p pc 2π(1973 eV ˚ ) A 2(0. With this light.
1. t) = ψ(x. Gasiorowicz Chapter 1 Rohlf Chapter 5 Griﬃths 1. The ﬁelds obey the wave equation. t)2 (We will overcome the problem that this probability is 1 everywhere for our simple wavefunction. Much of what we do for the rest of the course will be deduced from the paragraph above. Chapter
.) We have just put in most of the physics of Quantum Mechanics. The real and imaginary parts are out of phase like the EM ﬁelds. ¯ We will use a complex probability amplitude ψ(x.3 CohenTannoudji et al. • Free particles are represented by complex wave functions with a relationship between their particle properties – energy and momentum. however. • The absolute square of the wavefunction gives the probability distribution function. is proportional to the square of the ﬁelds. For both particles the wavelength is given by h λ= p and the frequency by E = hν = hω. although the details of the ﬁeld will vary a bit because electrons and photons are somewhat diﬀerent kinds of particles. • We can make superpositions of our free particle wave functions to make states that do not have deﬁnite momentum. We will ﬁnd that any state can be made from the superposition of free particle states with diﬀerent momentum. Our input came from deBroglie and Planck. Lets summarize the physics input again. P (x. t) ∝ ei(kx−ωt) = ei(px−Et)/¯
The probability to ﬁnd an electron is equal to the absolute square of the complex probability amplitude. We will use the same ideas for electrons. Quantum Mechanics only tells us the probability. The E and B ﬁelds are 90 degrees out of phase and both contribute to the intensity. and hence the probability to ﬁnd a photon. the intensity. with support from experiments. physics now only tells us the probability for some quantum events to occur. The ﬁelds from two slits can add constructively or destructively giving interference patterns. The traveling wave with momentum p and energy E then is
h ψ(x. and their wave properties – frequency and wavelength given by Planck and deBroglie. We have lost the complete predictive power of classical physics. t) for the electron.2.98
3
The Solution: Probability Amplitudes
For EM waves. We now have a waveparticle duality for all the particles.
we can multiply them by adding the exponents. eikx e−iωt = ei(kx−ωt)
3.
Similarly the phase goes through 2π in one period τ in time.1
3. but.99
3. ωτ = 2π
. They are often called a phase factor. One of the most common mistakes in test problems is to forget to take the complex conjugate when computing a probability. We can write sin θ =
eiθ −e−iθ 2i
and cos θ =
eiθ +e−iθ . c2 = c∗ c = (a − ib)(a + ib) = a2 + iab − iab + b2 = a2 + b2 This give the magnitude squared of the complex number. The absolute square is always real. (We choose a and b to be real numbers. 2
As with other exponentials. (Just change the sign of all the i.1.2
Review of Traveling Waves
A normal traveling wave may be given by cos(kx − ωt). A complex number c = a + ib consists of a real part a and an imaginary part ib. eiθ e
−iθ
= cos θ + i sin θ = cos θ − i sin θ
You can verify that the absolute square of these exponentials is always 1. you must make sure you use complex numbers correctly. So the wavelength λ satisﬁes kλ = 2π. The phase of the wave goes through 2π in one wavelength in x. The complex conjugate of c is c∗ = a − ib.1.1
Derivations and Computations
Review of Complex Numbers
This is a simple review. We will use complex exponentials all the time.) i is the square root of 1.) The absolute square of a complex number is calculated by multiplying it by its complex conjugate.
2
Sample Test Problems
1.
There is no reason to memorize these equations.100 ω is the angular frequency. At time t = 0. If we compute the phase velocity by taking Δx . 2. Write down the two (unnormalized) free particle wave functions for a particle of kinetic energy E. k
ω k. there is a peak at x = 0.)
(The phase velocity for the nonrelativistic case is vp =
3. Lets see how fast one of the peaks of the wave moves. This is the peak for which the argument of cosine is 0. we have ¯ k = p. This is called the phase velocity.
That is. They should be obvious. The frequency ν increases by 1 every cycle so ω = 2πν. and E = h ¯ ω(k) =
so
h ¯ 2 k2 h ¯ k2 E = = h ¯ 2m¯ h 2m
You may remember that a pulse will move at the group velocity which is given by vg = dω dk = h ¯k p 2¯ k h = = .
In nonrelativistic QM. E = hω. At time t = 1. It changes by 2π every cycle.
. one of the peaks of this wave travels with a velocity of v= ω 2πν = 2π = νλ k λ
p2 2m . the argument is zero when kx = ωt or at x = ω . Include the proper time dependence and expressions for other constants in terms of E. 2m m m
p 2m . we get k Δt vphase = ω .
so we will take the limit that L → ∞.)
. We do not want to limit our states in x. every wave number is allowed so the sum turns into an integral.6.
∞ ∞
f (x)f (x)dx =
−∞ −∞
∗
A∗ (k)A(k)dk
We understand f (x) as a wave packet made up of deﬁnite momentum terms eikx .101
4
Wave Packets
Gasiorowicz Chapter 2 Rohlf Chapters 5 Griﬃths Chapter 2 CohenTannoudji et al.2) 1 f (x) = √ 2π with coeﬃcients which are computable. In that limit. t)dx = 1
−∞
To make a wave packet which is localized in space. t) = ψ(x. The coeﬃcient of each term is A(k).6. The probability for a particle to be found in a region dx around some value of x is f (x)2 dx. t)ψ(x. we must add components of diﬀerent wave number.1) to compose any function f (x) when we limit the range to −L < x < L. Chapter
4. We would like a state which is localized and normalized to one particle. Recall that we can use a Fourier Series (See section 4. It is not ¯ ¯ localized since P (x. The probability for a particle to have wave number in region dk around some value of k is A(k)2 dk. 1 A(k) = √ 2π
∞ ∞
A(k)eikx dk
−∞
f (x)e−ikx dx. (Remember that p = hk so the momentum distribution is very closely related. t)2 = 1 everywhere.
∞
ψ ∗ (x. The result is the very closely related Fourier Transform (See section 4.
−∞
The normalizations of f (x) and A(k) are the same (with this symmetric form) and both can represent probability amplitudes.1
Building a Localized SingleParticle Wave Packet
We now have a wave function for a free particle with a deﬁnite momentum p
h ψ(x. t) = ei(px−Et)/¯ = ei(kx−ωt)
where the wave number k is deﬁned by p = hk and the angular frequency ω satisﬁes E = hω. We work with ¯ k for a while for economy of notation.
6. A Gaussian packet: A(k) =
1 √ a
for k0 −
a 2
< k < k0 +
a 2
and 0 elsewhere. We will show later that a Gaussian is the best one can do to localize a particle in position and momentum at the same time. In both of these cases of f (x) (transformed from a normalized A(k) localized in momentum space) we see
. x
The Fourier Transform of a Gaussian (See section 4. ∞ ∞
A(k) dk =
2 −∞
2α π
e−2α(k−k0 ) dk =
−∞
2
2α π
π =1 2α
So now we take the Fourier Transform of (1) right here. the single slit gives us a square localization in position space and the F.102
4. A “square” packet: A(k) = 2. π
These are both localized in momentum about p = hk0 .
2α 1/4 −α(k−k0 )2 e . If you square this. it should ax remind you of a single slit diﬀraction pattern! In fact. ¯ Check the normalization of (1). is this sin(x) function. 1.3)
∞
dx e−ax =
2
−∞
π a.6.4) wave packet A(k) = f (x) = 1 2πα
1/4
2α 1/4 −α(k−k0 )2 e π
is
eik0 x e− 4α
x2
also a Gaussian. f (x) = 1 √ 2π
∞
−∞
1 1 A(k)eikx dk = √ √ 2π a
k0 + a 2 k0 − a 2
k0 + a 2
eikx dk
k0 − a 2
f (x) f (x)
= =
1 1 ik0 x iax/2 1 1 ikx √ e e e = √ − e−iax/2 ix 2πa 2πa ix 1 1 ik0 x ax a ik0 x 2 sin ax 2 √ e e 2i sin = 2 2π ax 2πa ix
2 sin( ax ) 2 Note that is equal to 1 at x = 0 and that it decreases from there.2
Two Examples of Localized Wave Packets
Lets now try two examples of a wave packet localized in k and properly normalized at t = 0.T.
∞
−∞
1 A(k)2 dk = a
k0 + a 2
dk =
k0 − a 2
1 a=1 a
Check the normalization of (2) using the result for a deﬁnite integral of a Gaussian (See section 4.
but.
ΔpΔx ≥
h ¯ 2
. We achieved this by making wave packets which are superpositions of states with deﬁnite momentum. σx σk = = √ α 1 √ 4α
We can again see that as we vary the width in kspace. while localized. 2 a a This gives us ΔkΔx = 4π which certainly satisﬁes the limit above. then ¯ Δp = hΔk. That is ΔkΔx ≥ 1 . We will prove this later. So the width is twice this or Δx = 4π . If we translate into momentum p = hk. h • and a packet function which is localized in x. Note that if we change the width of A(k). 2 For the “square” packet the full width in k is Δk = a. The width in x is a little hard to deﬁne. lets use the ﬁrst node in the probability found at ax = π or x = 2π . the width in xspace varies to keep the product constant. For the Gaussian wave packet. We see that we can have states which are localized both in position space and momentum space.
4.4). We have achieved our goal of ﬁnding states that represent one free particle. The wave packets.6. • eik0 x – a wave corresponding to momentum ¯ k0 . 1 σx σk = 2 The Gaussian wave packet gives the minimum uncertainty. have some width in x and in p. the width of f (x) changes to keep the uncertainty product constant. we can rigorously read the RMS width of the probability distribution as was done at the end of the section on the Fourier Transform of a Gaussian (See section 4. ¯ So the Heisenberg Uncertainty Principle states.3
The Heisenberg Uncertainty Principle
The wave packets we tried above satisfy an uncertainty principle which is a property of waves.103 • A coeﬃcient which correctly normalizes the state to 1.
up (x) = √ 2π¯ h Similarly. If we try to make a particle with a deﬁnite momentum. (in position space) our formula for it is 1 h eipx/¯ . If we deﬁne up (x) to be the state with deﬁnite momentum p.4
Position Space and Momentum Space
We can represent a state with either ψ(x) or with φ(p). We have the symmetric Fourier Transform.104 It says we cannot know the position of a particle and its momentum at the same time and tells us the limit of how well we can know them. we get the Fourier Transforms. f (x) = 1 √ 2π 1 √ 2π
∞
A(k)eikx dk
−∞ ∞
A(k) =
f (x)e−ikx dx
−∞
When we change variable from k to p. its momentum becomes uncertain. its probability distribution spreads out over space.
4. the state (in momentum space) with deﬁnite position x is 1 h e−ipx/¯ vx (p) = √ 2π¯ h These states cannot be normalized to 1 but they do have a normalization convention which is satisﬁed due to the constant shown. We can (Fourier) transform from one to the other. Our Fourier Transform can now be read to say that we add up states of deﬁnite momentum to get ψ(x)
∞
ψ(x) =
−∞
φ(p)up (x)dp
.
1 ψ(x) = √ 2π¯ h 1 φ(p) = √ 2π¯ h
∞ h φ(p)eipx/¯ dp −∞ ∞ h ψ(x)e−ipx/¯ dx
−∞
These formulas are worth a little study. If we try to localize a particle to a very small region of space.
4) later. We can do the Fourier Transform to position space. We will ﬁnd that there are other ways to represent Quantum states.105 and we add up states of deﬁnite position to get φ(p). For a photon. including the time dependence. the state with deﬁnite 1 h momentum p0 .
4.5
Time Development of a Gaussian Wave Packet *
So far. lets expand ω(k) around the center of the wave packet in kspace. Using the notation of Dirac. We will now put time back into the wave function and look at the wave packet at later times. E = 2m . might be written simple as ψ . this just means that the energy depends on the momentum. This was a preview. we have performed our Fourier Transforms at t = 0 and looked at the result only at t = 0. E = pc. We will see that the behavior of photons and nonrelativistic electrons is quite diﬀerent. so ¯ ω = 2m . t) =
−∞
A(k)ei(kx−ω(k)t) dk
We write explicitly that ω depends on k.
∞
φ(p) =
−∞
ψ(x)vx (p)dx
There is a more abstract way to write these states. ω(k) = ω(k0 ) + dω dk (k − k0 ) +
k0
1 d2 ω 2 dk 2
(k − k0 )2
k0
. and hence ω = 2m . The arbitrary state represented by either ψ(x) or φ(p). Assume we start with our Gaussian (minimum uncertainty) wavepacket A(k) = e−α(k−k0 ) at t = 0. We will spend more time on Dirac Braket notation (See section 5. For an nonrelativistic h ¯ p2 h2 k 2 ¯ hk 2 ¯ h electron. up0 (x) = √2π¯ eip0 x/¯ might be written as h p0 and the state with deﬁnite position x1 . The actual wave function ψ(x) would be written as ψ(x) = xψ . vx1 (p) =
h √ 1 e−ipx1 /¯ 2π¯ h
might be written
x1 . For our free particle.
∞
2
ψ(x. This gives us the amplitude to be at x for any value of x. so ¯ ω = hkc. To cover the general case. and hence ω = kc.
∞
f (x) =
n=0
An cos
nπx nπx + Bn sin L L n=1
∞
Since the sines and cosines can be made from the complex exponentials.
−α(x−vg t)2
We see that the photon will move with the velocity of light and that the wave packet will not disperse. The RMS width is σ = α2 +
ht 2 ¯ 2m .6.
∞
f (x) =
n=−∞
an e
inπx L
The exponentials are orthogonal and normalized over the interval (as were the sines and cosines)
L
1 2L
e
−L
inπx L
e
−imπx L
dx = δnm
so that we can easily compute the coeﬃcients. the wave packet moves with the correct group velocity. L). vg = packet spreads with time. because β = 0. For the NR electron. Wave packets that are very localized in space spread rapidly.
but the wave
A wave packet naturally spreads because it contains waves of diﬀerent momenta and hence diﬀerent velocities.
4. using negative n to get the other term. t)2 = =
−(x−vg t)2 π ei(k0 x−ω0 t) e 4(α+iβt) α + iβt
hk0 ¯ m
and β =
h ¯ 2m .
L
1 an = 2L
f (x)e
−L
−inπx L
dx
.5). p m.6
4. we can equally well use them for our basis for expansion. For the NR electron. in terms of sines and cosines also periodic on that interval.106 We anticipate the outcome a bit and name the coeﬃcients. vg = Performing the Fourier Transform (See section 4. t) ψ(x.1
Derivations and Computations
Fourier Series *
Fourier series allow us to expand any periodic function on the range (−L. vg = c and β = 0. we get ψ(x. ω(k) = ω0 + vg (k − k0 ) + β(k − k0 )2 For the photon. This has the nice simpliﬁcation of having only one term in the sum.
π α2 + β 2 t2
e 2(α2 +β2 t2 ) .6.
then A(k) will also be normalized with this (symmetric) form of the Fourier Transform. if f (x) is a probability amplitude in positionspace.
. Our sum over n becomes an integral over k. L
As L → ∞. we can make the transform come out with the constants we want. As we do this we will use the wave number k= nπ . A(k) can be a probability amplitude (in kspace). Functions are available in computer libraries to return this important integral. we will expand the interval used L → ∞.6.6.
f (x)e
−L
−inπx L
dx. k can take on any value.107 In summary.
4.
4. f (x) = 1 √ 2π 1 √ 2π
∞
A(k)eikx dk
−∞ ∞
A(k) =
f (x)e−ikx dx
−∞
This is just the extension of the Fourier series to all x.. the Fourier series equations we will use are
∞
f (x) =
n=−∞
an e
inπx L
and
L
1 an = 2L We will expand the interval to inﬁnity. π dk = dn. implying we will have a continuous distribution of k. With other limits. If f (x) is normalized. L √ La n If we deﬁne A(k) = 2 π . Thus.2
Fourier Transform *
To allow wave functions to extend to inﬁnity. the integral cannot be done analytically but is tabulated.3
Integral of Gaussian
This is just a slick derivation of the deﬁnite integral of a Gaussian from minus inﬁnity to inﬁnity.
−∞
2
Integrate over both x and y so that
∞ ∞ ∞ ∞
I =
−∞
2
dx e
−ax2 −∞
dy e
−ay 2
=
−∞ −∞
dxdy e−a(x
2
+y 2 )
. a
Deﬁne I=
∞
dx e−ax .
∞ ∞
I = 2π
0
2
rdr e
−ar 2
=π
0
2 2 1 d(r2 ) e−ar = π − e−ar a
∞
=
0
π a
Now just take the square root to get the answer above.
2
−∞
Now we will transform the integral a few times to get to the standard deﬁnite integral of a Gaussian for which we know the answer.
Transform to polar coordinates. The Fourier Transform formula is π 1 f (x) = √ 2π 2α π
1/4 ∞
e−α(k−k0 ) eikx dk. ∂ ∂a
∞
dx e−ax =
−∞
2
∂ ∂a
π a
∞
dx x2 e−ax =
−∞
2
1 2a
π a
4.4
Fourier Transform of Gaussian *
We wish to Fourier transform the Gaussian wave packet in (momentum) kspace A(k) = 2α 1/4 −α(k−k0 )2 e to get f (x) in position space.
∞
dx e−ax =
−∞
2
π . a
Other forms can be obtained by diﬀerentiating with respect to a.6. First.108 The answer is
∞
dx e−ax =
−∞
2
π . k = k − k0
.
we get P (x) = 1 − x2 e 2α . The RMS deviation. 2πα
. f (x) = α 2π 3
1/4 ∞
eik0 x
−∞
e−α(k − 2α ) e− 4α dk
ix 2
x2
That term can be pulled outside the integral since it doesn’t depend on k.
∞
f (x) dx =
2 −∞
1 2πα
∞
e− 2α dx =
−∞
x2
1 √ 2απ = 1 2πα
Given a normalized A(k). We plan a term like e−αk so we deﬁne ix . Lets write out the planned exponent to see what we are missing. we get a normalized f (x).
2
So now we have the standard Gaussian integral which just gives us f (x) f (x) = = α 2π 3 1 2πα
1/4
π ik0 x − x2 e e 4α α eik0 x e− 4α
x2
1/4
Lets check the normalization. −α k −
x2
2
ix 2α
2
= −αk 2 + ik x +
x2 4α
We need to multiply by e− 4α to cancel the extra term in the completed square. or standard deviation of a Gaussian can be read from the distribution.
(x−X)2 1 P (x) = √ e− 2σ2 2 2πσ
Squaring f (x). f (x) = α 2π 3 α 2π 3
1/4 ∞
e
1/4
ik0 x −∞ ∞
e−α(k−k0 ) ei(k−k0 )x dk
2
f (x) =
eik0 x
−∞
e−αk eik x dk
2
Now we want to complete the square in the exponent inside the integral. α f (x) = 2π 3
1/4
e
x ik0 x − 4α
2
∞
e
e−αk dk
−∞ π α. k =k − 2α Again dk = dk = dk.109 which does nothing really since dk = dk.
110 Reading from either the coeﬃcient or the exponential we see that √ σx = α For the width in kspace. To cover the general case. σx σk = 1 2
Translating this into momentum. σx σp = In fact the Uncertainty Principle states that σx σp ≥ h ¯ 2 h ¯ 2
so the Gaussian wave packets seem to saturate the bound!
4.
∞
2
ψ(x. the width in xspace varies to keep the product constant. Make the substitution k = k − k0 giving A(k ) = e−αk . We are not interested in careful normalization here so we will drop constants. For our free particle. lets expand ω(k) around the center of the wave packet in kspace. we get P (k) = 1 σk = √ . π Reading from the coeﬃcient of the exponential. we get the limit of the Heisenberg Uncertainty Principle. dω 1 d2 ω k0 (k − k0 ) + k (k − k0 )2 ω(k) = ω(k0 ) + dk 2 dk 2 0 We anticipate the outcome a bit and name the coeﬃcients. t) =
−∞
A(k)ei(kx−ω(k)t) dk
We write explicitly that w depends on k.
∞
ψ(x. this just means that the energy depends on the momentum.5
Time Dependence of a Gaussian Wave Packet *
2
Assume we start with our Gaussian (minimum uncertainty) wavepacket A(k) = e−α(k−k0 ) at t = 0. ω(k) = ω0 + vg (k − k0 ) + β(k − k0 )2 We still need to do the integral as before.6. 2α −2α(k−k0 )2 e . 4α We can see that as we vary the width in kspace. t)
=
ei(k0 x−w0 t)
−∞
A(k )ei(k x−vg t) e−ik
2
βt
dk
. Factor out the constant exponential that has no k dependence.
6
Numbers
The convenient unit of energy (mass and momentum too) is the electron volt. k x → k (x − vg t).111
∞
ψ(x. α= This combination saves a lot of work.602 × 10−19 Joule Use the ﬁne structure constant to avoid CGS units which are used in the textbook. h ¯ c = 1973 eV˚ = 197.3MeV/c2 mn = 939.6.529 × 10−10 m αme c mp = 938. Dropping the constants.511MeV/c2
. 1eV = 1. t)
=
e
i(k0 x−w0 t) −∞ ∞
e−αk ei(k x−vg t) e−ik
2
2
βt
dk
ψ(x. We can then write down the answer ψ(x.602 × 10−12 erg = 1.6MeV/c
2
e2 = 1/137 h ¯c
me = 0. t)2 = = =
−(x−vg t)2 π ei(k0 x−ω0 t) e 4(α+iβt) α + iβt −(x−vg t)2 π π ei(k0 x−ω0 t) e 4(α+iβt) α + iβt α − iβt
π α2 + β 2 t2
e 2(α2 +β2 t2 )
−α(x−vg t)2
4. t)2 ψ(x. t)
=
ei(k0 x−w0 t)
−∞
e−[α−iβt]k ei(k x−vg t) dk
2
We now compare this integral to the one we did earlier (so we can avoid the work of completing the square again). t) ψ(x.3MeVF A 1˚ = 1. we had
∞
f (x) = e
ik0 x −∞
e−αk eik x dk = eik0 x e− 4α
2
x2
Our new integral is the same with the substitutions k0 x → k0 x − ω0 t. a0 = h ¯ = 0. and α → (α + iβt).0 × 10−10 m A 1Fermi = 1.0 × 10−15 m The Bohr radius gives the size of the Hydrogen atom.
and we transform to position space.7 The Dirac Delta Function
The Dirac delta function is zero everywhere except at the point where its argument is zero.7. It picks of the value of the function f (x) at the point where the argument of the delta function vanishes. If we make a wave packet in pspace using the delta function. δ(x − x0 ) 1
∞
−∞
1 h h δ(p − p0 )eipx/¯ dp = √ eip0 x/¯ 2π¯ h
4. δ(p − p0 ) 1 h Its Fourier transform is ψp (x. This is a state of deﬁnite momentum written in momentum space.7
4.1
Examples
The Square Wave Packet
Given the following one dimensional probability amplitude in the position variable x. ψ(x) = √ 2π¯ h we just get the state of deﬁnite p. t) = √2π¯ ei(px−Et)/¯ h This is a state of deﬁnite position written in position space.
−∞
This is the deﬁnition of the delta function. 1 ψ(x) = √ 2a for −a < x < a.112 4.
.6. it is just the right kind of inﬁnity so that
∞
dx f (x) δ(x) = f (0).
∞
dx f (x) δ(x − a) = f (a)
−∞
The transformation of an integral allows us to compute
∞
dx f (x) δ(g(x)) =
−∞
1
dg  dx 
f (x)
g(x)=0
the eﬀect of the argument being a function. A simple extension of the deﬁnition gives. Show that the uncertainty principle is roughly satisﬁed. compute the probability distribution in momentum space. otherwise ψ(x) = 0. At that point.
we must use light with a wavelength smaller than the size of the atom. 2 1 ψ(x) = ( α ) 4 e−αx /2 π
4.2
The Gaussian Wave Packet *
Given the following one dimensional probability amplitude in the position variable x. You can no longer
. compute the probability distribution in momentum space.
a
φ(k)
=
1 √ 2π
−a
1 √ e−ikx dx 2a
a
φ(k) φ(k) φ(k)
= = =
−1 −ikx 1 √ e 4πa ik −a 1 −ika √ − eika e ik 4πa 1 √ [−2i sin ka] = − ik 4πa 1 sin(ka) πa k
Now estimate the width of the two probability distributions.3
The Dirac Delta Function Wave Packet *
Given the following one dimensional probability amplitude in the position variable x. compute the probability distribution in momentum space. Show that the uncertainty principle is roughly satisﬁed.7.25 micron level. With normal light.7.
∞
a
ψ ψdx =
−∞ −a
∗
1 dx = 1 2a
Take the Fourier Transform. ψ(x) = δ(x − x0 )
4.113 Its normalized. Δx = 2a 1 sin2 (ka) φ(k)2 = πa k2 2π Δk = a ΔxΔk = 4π
4. once a surface is polished down to the .4
Can I “See” inside an Atom
To see inside an atom.7. Show that the uncertainty principle is roughly satisﬁed. it looks shiny.
We learn about the internal structure of the atoms by scattering particles oﬀ them. We can use the uncertainty principle to estimate the minimum energy for Hydrogen. The binding energy per nucleon is a few MeV. but we can use many atoms of the same kind. A
2π¯ h 0. causing p to increase on average. blowing them apart.1 ˚.
4.1
This is more than enough kinetic energy to blow the atom apart. r p ≥ ≥ Δx Δp = h ¯ 2r
. We again can just use lots of nuclei to allow us to learn about internal nuclear structure. A similar calculation can be made with the uncertainty principle. You can’t “see” inside. We can probe atoms with high energy photons (for example). so. If the electron were conﬁned to a smaller volume.
4. So to see inside the atom. we will also blow nuclei apart to look carefully inside them. we would need light with λ = p pc = =
h p
= 0.1F ) = 1000 MeV. This is not a perfect calculation but it is more correct than the Bohr model. The idea is that the radius must be larger than the spread in position.7.5
Can I “See” inside a Nucleus
hc ¯ In a similar fashion to the previous section. so this will still blow it apart. So we can’t “watch” the inside of an atom.7. These will blow the atoms apart.1 2π1973 2π¯ c h = = 120000 eV 0.114 see defects.1 0. Δp would increase. The energy would increase not decrease. h ¯ 2 h ¯c Δ(pc)Δx ≥ 2 h ¯c ΔEγ ≥ 2Δx h ¯c Eγ ≥ = 10000eV 2(0. and the momentum must be larger than the spread in momentum.1˚ ) A ΔpΔx ≥ The binding energy is 13 eV. Eγ ≥ 2(0.6
Estimate the Hydrogen Ground State Energy
The reason the Hydrogen atom (and other atoms) is so large is the essentially uncertainty principle.
pr E E = = = h ¯ α¯ cp h p2 − 2m h ¯ p2 − αcp 2m α¯ c h p2 − 2m r
Diﬀerentiate with respect to p and set equal to zero to get the minimum. dE dp p E p − αc = 0 m = αmc α2 mc2 α2 mc2 − α2 mc2 = − = −13.6 eV = 2 2 =
Note that the potential energy is just (2) times the kinetic energy (as we expect from the Virial Theorem).3M eV 2 2 r2 2m 2mr 2mc 2(940M eV )(4F )2
.8
Sample Test Problems
1. Do the same for an electron. A nucleus has a radius of 4 Fermis. We can also estimate the radius. r= h ¯ 1973eV ˚ (137) A h ¯ h ¯c = = = = 0. The ground state energy formula is correct.3M eV F )2 = = = ≈ 1. the energy would go up. Answer ΔpΔx ≈ ¯ h pr ≈ ¯ h Try nonrelativistic formula ﬁrst and verify approximation when we have the energy. A If it were not spread out. It is not moving in a circular orbit as Bohr hypothesized.53˚ A 2 p αmc αmc 511000eV
The ground state of Hydrogen has zero (orbital) angular momentum. V (r) = − α¯ c h e2 =− r r
Lets estimate the energy E= and put in the eﬀect of the uncertainty principle. E= p2 h ¯2 (¯ c)2 h (197.
4.115 This is our formula for the potential energy in terms of the dimensionless ﬁne structure constant α. The electron just has a probability distribution that is spread out over about 1 ˚. Use the uncertainty principle to estimate the kinetic energy for a neutron localized inside the nucleus.
* Given the following one dimensional probability amplitudes in the position variable x. * Find the one dimensional wave function in position space ψ(x) that corresponds to φ(p) = for −b < p < b.
2
b ψ(x) = ( α ) 4 e−αx π c ψ(x) = δ(x − x0 )
/2
5. Show that the uncertainty principle is roughly satisﬁed. a ψ(x) =
√1 2a
1
for −a < x < a.
1 √ 2b
. Use the uncertainty principle to estimate the minimum value of V0 needed for the neutron to be bound to the nucleus. * Assume that the potential for a neutron near a heavy nucleus is given by V (r) = 0 for r > 5 Fermis and V (r) = −V0 for r < 5 Fermis. This makes it easier.) Minimize. 3. and φ(p) = 0 otherwise. 7. otherwise ψ(x) = 0.51 MeV so it WILL be relativistic.3M eV F h ¯c = ≈ 50M eV r 4F
2. 2 6. Answer ΔpΔx ≈ ¯ h pr ≈ ¯ h 2 e p e p − = − p E= 2m r 2m h ¯
2 2 2
(We could have replaced p equally well.116 This is much less than 940 MeV so the nonrelativistic approximation is very good. dE p e2 = − =0 dp m h ¯ me2 p= h ¯ e2 m2 e 4 me4 me4 me4 me4 p2 − p= − 2 = − 2 =− 2 E= 2m h ¯ 2m¯ 2 h h ¯ 2¯ 2 h h ¯ 2¯ h e2 α= h ¯c e2 = α¯ c h 1 2 2 E = − α mc 2 4. compute the probability distribution in momentum space. pr ≈ ¯ h E = pc = 197. Use the Heisenberg uncertainty principle to estimate the ground state energy for a particle of mass m in the potential V (x) = 1 kx2 . The electron energy will be higher and its rest mass is only 0. * Find the one dimensional wave function in position space ψ(x) that corresponds to φ(p) = δ(p − p0 ). Use the uncertainty principle to estimate the ground state energy of Hydrogen.
The hydrogen atom is made up of a proton and an electron bound together by the Coulomb 2 potential. * A particle is in the state ψ(x) = Ae−αx momentum between p and p + dp?
2
/2
. Use the uncertainty principle to estimate the energy and the radius of the ground state of muonic hydrogen. It is also possible to make a hydrogenlike atom from a proton and a r muon. ψ(p) = 0 elsewhere. * Assume that a particle is localized such that ψ(x) = √a for 0 < x < a and that ψ(x) = 0 elsewhere. What is ψ(x)? What is the 2a probability to ﬁnd the particle between x and x + dx? 14. * Assume that φ(p) = √1 for p < a and φ(p) = 0 elsewhere. What is the probability for the particle to have a
−e2 r .
¯ (b) ψ(p) = δ(p − p0 ) 2 1 ¯ (c) ψ(p) = ( α ) 4 e−αp /2
π
16. 15. Show that the uncertainty principle is satisﬁed.
. Use the uncertainty principle to estimate the width of the central maximum of the diﬀraction pattern in terms of the variables given. * Given the following one dimensional probability amplitudes in the momentum representation. Is the state correctly normalized? Explain why. V (r) = −e . 10. * The wavefunction of a particle in position space is given by ψ(x) = δ(x − a). 11. ¯ (a) ψ(p) =
√1 2a
¯ for −a < p < a. The resulting diﬀraction pattern is viewed on screen which is a distance d from the slit. * Assume that φ(p) = δ(p − p0 ). What is ψ(x)? What is < p2 >? What is < x2 >? 17. Find the wavefunction in momentum space. A hydrogen atom has the potential V (r) = ground state energy.117
1 8.
12. compute the probability amplitude in the position representation.
Use the uncertainty principle to estimate the
13. What is the probability for the particle to have a momentum between p and p + dp?
9. The force binding the muon to the proton is identical to that for the electron but the muon’s mass is 106 MeV/c2 . A beam of photons of momentum p is incident upon a slit of width a. ψ(x).
t) = √ ei(p0 x−E0 t)/¯ . when we operate with px get p0 times the same wave function.
.5. t)dp
5.1) that this works by explicit calculation. p(op) up0 (x. t) = p0 up0 (x. we
This means that for these deﬁnite momentum states. t). t) = p
(op) −∞
φ(p) up (x. Our state of deﬁnite momentum p0 (and deﬁnite energy E0 ) is 1 h up0 (x. we will look at wave functions with deﬁnite momentum.1) is a simple diﬀerential operator like understand to diﬀerentiate everything to the right of it with respect to x.6.
∞ ∞
p
(op)
ψ(x.
∂ ∂x . They will also be used in almost any Quantum Physics calculation. t)dp =
−∞
φ(p) p up (x. t)dp
it gives us the right p for each term in the integral. We ﬁnd that this is true for the following momentum operator.
∞
ψ(x. If we take our momentum operator and act on a arbitrary state. 2π¯ h We can build any other state from superpositions of these states using the Fourier Transform.1
The Momentum Operator
(op)
We determine the momentum operator by requiring that.
(op)
p(op) =
h ¯ ∂ i ∂x
We can verify (See section 5. An example of a linear operator (See section 6.118
5
Operators
Operators will be used to help us derive a diﬀerential equation that our wavefunctions must satisfy. multiplying by px is the same as multiplying by the variable p.1
Operators in Position Space
To ﬁnd operators for physical variables in position space. t) =
−∞
φ(p) up (x. t)
on up0 (x.1.
which we
5. This will allow us to compute expectation values for any variable we can represent by an operator.
H= p2 + V (x) 2m
H (op) = −
h ¯ 2 ∂2 + V (x) 2m ∂x2
Since the potential energy just depends on x.2
Operators in Momentum Space
If we want to work in momentum space.
E (op) = i¯ h
∂ ∂t
5. we need to look at the states of deﬁnite position to ﬁnd our operators. its easy to use.1.1.4
The Hamiltonian Operator
We can develop other operators using the basic ones. Angular momentum operators will later be simply computed from position and momentum operators.3
The Position Operator
What about the position operator. We will use the Hamiltonian operator which. x(op) ? The answer is simply
x(op) = x
when we are working in position space with up0 (x.2 The Energy Operator
We can deduce and verify (See section 5. for our purposes.6.1.
5. The state (in momentum space) with deﬁnite position x0 is vx0 (p) = √ The operators are 1 h e−ipx0 /¯ 2π¯ h
.2) the energy operator in the same way.119 5. t) =
h √ 1 ei(p0 x−E0 t)/¯ 2π¯ h
(as we have been above). is the sum of the kinetic and potential energies. This is the nonrelativistic case.
5.
7.4) shown above is a convenient way to represent the expectation value of a variable given some state. * See Example 5. CohenTannoudji et al. t).3
Expectation Values
Operators allow us to compute the expectation value of some physics quantity given the wavefunction. The expectation value of p in the state ψ is
∞
p
ψ
= ψpψ =
−∞
ψ ∗ (x)p(op) ψ(x)dx
The Dirac Braket notation (See section 5.1: A particle is in the state ψ(x) = value of p?*
1/4 ik0 x − x2 1 e e 4α . let its operator act on ψ(x). The (op) notation used above is usually dropped. use of the operator is implied (except in state written in terms of p like φ(p)). 2πα
What is the expectation
. Chapter
5. the normal way to compute the expectation value of f (x) is
∞ ∞
f (x)
ψ
=
−∞
P (x)f (x)dx =
−∞
ψ ∗ (x)ψ(x)f (x)dx. If we see the variable p.
∞
f (x)
ψ
=
−∞
ψ ∗ (x) f (x) ψ(x)dx
If the variable we wish to compute the expectation value of (like p) is not a simple function of x.120
x(op) = i¯ h
∂ ∂p
and p(op) = p.
We can move the f (x) between just before ψ anticipating the use of linear operators. If a particle is in the state ψ(x. Gasiorowicz Chapter 3 Griﬃths doesn’t cover this.
5
Commutators
Operators (or variables in quantum mechanics) do not necessarily commute. x] ≡ px − xp
(using p and x as examples. p A state with deﬁnite position x. Chapter
5. We deﬁne the commutator to be
[p. we dot the state of deﬁnite x into our state ψ. x The “dot product” between two abstract states ψ1 and ψ2 . We can see our ﬁrst example of that now that we have a few operators. φ(p) = pψ
5. the expectation value of v in an arbitrary state ψ is
∞
ψvψ =
−∞
ψ ∗ (x)v (op) ψ(x)dx
The expectation values of physical quantities should be real. Gasiorowicz Chapter 3 Griﬃths Chapter 1 CohenTannoudji et al.
∞
ψ1 ψ2 =
−∞
∗ ψ1 ψ2 dx
To ﬁnd the probability amplitude for our particle to by at any position x. ψ(x) = xψ
To ﬁnd the probability amplitude for our particle to have a momentum p. Because p is represented by a diﬀerential operator.) We will now compute the commutator between p and x.121 For any physical quantity v.4
Dirac Braket Notation
A state with deﬁnite momentum p. we must do this carefully. Lets think of the commutator as a (diﬀerential) operator too. as
. we dot the state of deﬁnite x into our state ψ.
Chapter
5. To make sure that we keep all the ∂x that we need. We can compute the same commutator in momentum space. we get the commutator.* [E. * * * * See See See See Example Example Example Example 5. x]ψ(x) [p. x] = [p.6.7.1
Derivations and Computations
Verify Momentum Operator 1 1 h ¯ ∂ h h √ p(op) √ ei(p0 x−E0 t)/¯ = ei(p0 x−E0 t)/¯ i ∂x 2π¯ 2π¯ h h
.4: 5.
[p.122
∂ generally it will be. x]ψ(x)
= pxψ(x) − xpψ(x) = = h ¯ i
h ¯ ∂ h ¯ ∂ xψ(x) − x ψ(x) i ∂x i ∂x ∂ψ(x) ∂ψ(x) h ¯ −x ψ(x) + x = ψ(x) ∂x ∂x i
So.7. we will compute [p.7. x]φ = [p.5: Compute Compute Compute Compute the the the the commutator commutator commutator commutator [E.2: 5.3: 5.* of the angular momentum operators [Lx . Ly ].*
Gasiorowicz Chapter 3 Griﬃths Chapter 3 CohenTannoudji et al. [p. Physical variable with zero commutator have no uncertainty principle and we can know both of them at the same time. x]. xn ]. We will also use commutators to solve several important problems.* [p. i¯ h h ¯ i d d d ]φ = i¯ p φ − pφ h dp dp dp = i¯ (−φ) = h h ¯ φ i
The commutator is the same in any representation. x] =
h ¯ i
Later we will learn to derive the uncertainty relation for two variables from their commutator.
[p. t]. removing the ψ(x) we used for computational purposes.6
5. x]ψ(x) then remove the ψ(x) at the end to see only the commutator.7.
7.2
Verify Energy Operator 1 1 −iE0 i(p0 x−E0 t)/¯ h h e E (op) √ ei(p0 x−E0 t)/¯ = √ i¯ h h ¯ 2π¯ h 2π¯ h = E0 √ 1 2π¯ h
h ei(p0 x−E0 t)/¯
5.
∞
p
ψ
=
ψpψ =
−∞ ∞
ψ ∗ (x)p(op) ψ(x)dx
1/4
x2
=
−∞
1 2πα
1/2
e−ik0 x e− 4α
∞
h ¯ ∂ i ∂x
x2
1 2πα
1/4
eik0 x e− 4α dx
x2
=
1 2πα 1 2πα 1 2πα
h ¯ i h ¯ i h ¯ i
e−ik0 x e− 4α
−∞ ∞
x2
∂ ik0 x − x2 e e 4α dx ∂x ik0 eik0 x e− 4α − 2x − x2 e 2α 4α
x2
1/2
=
e−ik0 x e− 4α
−∞ ∞
x2
2x ik0 x − x2 e e 4α 4α
dx
1/2
=
ik0 e− 2α −
−∞
dx
The second term gives zero because the integral is odd about x = 0.1
Examples
Expectation Value of Momentum in a Given State
1/4 ik0 x − x2 1 e e 4α . ψpψ = 1 2πα 1 2πα
1/2
h ¯ i
∞
ik0 e− 2α dx
−∞
x2
1/2
ψpψ
=
√ h ¯ k0 2πα = hk0 ¯
Excellent.
.123 1 ¯ ip0 i(p0 x−E0 t)/¯ h 1 h h √ ei(p0 x−E0 t)/¯ e = p0 √ i ¯ h 2π¯ h 2π¯ h
5.6.7
5. 2πα
A particle is in the state ψ(x) =
What is the expectation value of p?
We will use the momentum operator to get this result.
x]xn−1 − xn p x(px)xn−2 + [p. t) ∂ ∂ − i¯ t h ∂t ∂t ψ(x. t]ψ(x. h ¯ h ¯ ∂ h ¯ ∂ n x ψ − xn ψ = nxn−1 ψ [p. t] = i¯ h
5.2 Commutator of E and t
Again use the crutch of keeping a wave function on the right to avoid mistakes. x]xn−1 = n xn−1 i
It is usually not wise to use the diﬀerential operators and a wave function crutch to compute commutators like this one. x]ψ(x. xn ]ψ = i ∂x i ∂x i
. x]xn−1 − xn p x2 pxn−2 + x[p.124 5. t) ψ(x. [p. [E. xn ] = = = = = = = = = pxn − xn p (px)xn−1 − xn p xpxn−1 + [p. [E. t) = 0
= 0. Remember that px = xp + [p. t) + i¯ t h h = i¯ ψ(x. Nevertheless. x]xn−1 − xn p x2 pxn−2 + 2[p.7. t) h Removing the wave function. x]xn−2 + [p.7. x]xn−1 − xn p xn p + n[p. we have the commutator. we can compute it that way. Use the known basic commutators when you can.7.
5. x]xn−1 − xn p h ¯ n[p. t)
= i¯ ψ(x. x].3
Commutator of E and x
Again use the crutch of keeping a wave function on the right to avoid mistakes.4
Commutator of p and xn
We can use the commutator [p. [E. x]xn−1 − xn p x3 pxn−3 + 3[p. t) = = Since
∂x ∂t
i¯ h
∂ ∂ x − xi¯ h ∂t ∂t ∂ ∂ h i¯ x − i¯ x h ∂t ∂t
ψ(x. t) = i¯ h ∂ ∂ t − ti¯ h ∂t ∂t ψ(x. x] to help us.
8
Sample Test Problems
1. Compute the RMS xwidth of this wave packet as a function of time. The absolute square of a wave function for a free particle is given as: ψ(x. So the components of angular momentum are Lz = xpy − ypx Lx = ypz − zpy Ly = zpx − xpz . [Lx .
. z]px − 0 − 0 + x[z. We wish to compute [Lx .7. zpx − xpz ] [ypz . zpx] − [ypz . xpz ] − [zpy . [x. The only operators that do not commute are the coordinates and their conjugate momenta.
5. but not if I have p to some power. Find the expected value of x2 as a function of time. py ] = 0 [pi . Ly ] which has all the coordinates and momenta in it.. y] = 0 [px . t)2 = 2π(a2
2 2 2 2 a e−a(x−vg t) /2(a +b t ) 2 t2 ) +b
Find the expected value of x as a function of time. Use the known basic commutators when you can. xn ] =
5.. Ly ] = = = = [ypz − zpy . pz ]py h ¯ (ypx − xpy ) = i¯ Lz h i h ¯ δij i
It is not necessary (or wise) to use the diﬀerential operators and a wave function crutch to compute commutators like this one. zpx] + [zpy .125 h ¯ n−1 nx i It works pretty well for this particular case. rj ] = So now we just need to compute. xpz ] y[pz . [p.5
Commutator of Lx and Ly
Angular momentum is deﬁned by L = r × p.
If a particle is in a state of deﬁnite energy.x] and [H. Which of the following are linear operators? • O1 ψ(x) = 1/ψ(x) • O2 ψ(x) = • O3 ψ(x) = x ψ(x) • O4 ψ(x) = −ψ(x + a) 4. For a free particle. what do these commutators tell you about how well we know the particle’s position and momentum? 5.p]. the total energy operator H is given by H = p2 /2m. Find the commutator [x. Find the commutator [p. eik0 x ] where k0 is a constant and the second operator can be expanded as eik0 x =
∞ n=0 (ik0 x)n . 7. p3 ]. Compute the commutator [H. x2 ] where H is the Hamiltonian for a free particle.126 2. 6. n!
3. Compute the commutators [H.
∂ψ(x) ∂x 2
.
− − h ¯ 2 ∂2 ∂ 1 1 h h √ ei(p0 x−E0 t)/¯ = i¯ √ ei(p0 x−E0 t)/¯ h 2 2m ∂x ∂t 2π¯ 2π¯ h h
The constant in front of the wave function can be removed from both sides. We will go ahead and do the diﬀerentiation.
6. we have p2 =E 2m ∂ h ¯ 2 ∂2 ψ = i¯ ψ h 2m ∂x2 ∂t Lets try this equation on our states of deﬁnite momentum. the kinetic energy operator has space derivatives. it is natural to try an energy equation. The Schr¨dinger o equation is the operator statement that the kinetic energy plus the potential energy is equal to the total energy. Its there for normalization. − −iE0 i(p0 x−E0 t)/¯ h ¯ 2 −p2 i(p0 x−E0 t)/¯ 0 h h e = i¯ h 2 e 2m ¯ h ¯ h p2 i(p0 x−E0 t)/¯ 0 h h e = E0 ei(p0 x−E0 t)/¯ 2m
. o Since the Energy operator has a time derivative. not part of the solution.127
6
The Schr¨dinger Equation o
Schr¨dinger developed a diﬀerential equation for the time development of a wave function.1
Deriving the Equation from Operators
For a free particle. and we expect the solutions to be traveling waves.
j(x. t) = ψ ∗ ψ and using the Schr¨dinger Equation. We can derive an equation showing conservation of probability (See section 6.
. but there is a net ﬂow along the direction of the momentum. t) = i¯ h 2m ∂t
We will use it to solve many problems in this course.2).2
The Flux of Probability *
In analogy to the Poynting vector for EM radiation. t) where H= is the Hamiltonian operator. p2 + V (x) 2m
Hψ(x. t) ∂j(x. t) + V (x)ψ(x. t) + V (x)ψ(x. t) ∇ ψ(x. So the Schr¨dinger Equation is. by diﬀerentiating o P (x.128
p2
0 Our wave function will be a solution of the free particle Schr¨dinger equation provided E0 = 2m . t) = h ¯ ∂ψ ∂ψ ∗ − ψ ψ∗ 2mi ∂x ∂x
This current can be computed from the wave function. t) + =0 ∂t ∂x This is the usual conservation equation if j(x. ∂P (x. we may want to know the probability current in some physical situation.5. t) =
−¯ 2 2 h ∂ψ(x. we have the Schr¨dinger Equation o
−¯ 2 ∂ 2 ψ(x.
Adding in potential energy. This o is exactly what we wanted. t) is identiﬁed as the probability current. the probability density is uniform over all space. For example.
6. this becomes. In three dimensions. t) = i¯ h 2m ∂x2 ∂t
or Hψ(x. in our free particle solution. So we have constructed an equation that has the expected wavefunctions as solutions. t) = Eψ(x. t) h ∂ψ(x. simply the statement (in operators) that the kinetic energy o plus the potential energy equals the total energy. in some sense. It is a wave equation based on the total energy.
for waves on a string or on water. Extending this analysis to 3 dimensions. t) ∂x
∂ ∂t
a
P (x. t) h + V (x)ψ(x. in eﬀect shifting the phase by 90 degrees as the 2nd derivative would do. t) dx = − ∂t
a b a
∂j(x. t) 2mi
6.129 If we integrate if over some interval in x
b b
∂P (x. These separated solutions can then be used to solve the problem in general. ∂ψ(x. however. t) + ∇ · j(r. relates the second space derivative to the second time derivative. Gasiorowicz Chapter 3 Griﬃths Chapter 1 CohenTannoudji et al. can be solved by separation of o variables. t) −¯ 2 ∂ 2 ψ(x. t)∇ψ(r.3
The Schr¨dinger Wave Equation o
The normal equation we get. ∂P (x. t) = 0 ∂t with
j(r. o the addition of the i relates the real part of the wave function to the imaginary part. he discovered new physics. t) = i¯ h 2 2m ∂x ∂t The Schr¨dinger equation is built for complex wave functions. t)
the equation says that the rate of change of probability in an interval is equal to the probability ﬂux into the integral minus the ﬂux out. The Schr¨dinger equation uses only the ﬁrst time derivative. like the Schr¨dinger Equation. o When Dirac tried to make a relativistic version of the equation. where the energy relation is a bit more complicated. Chapter
6. t)∇ψ ∗ (r.
.4
The Time Independent Schr¨dinger Equation o
Second order diﬀerential equations. t) =
h ¯ ψ ∗ (r. t) − ψ(r. t)dx = j(x = a. t) − j(x = b.
130 Assume that we can factorize the solution between time and space. they both must equal a constant. we call the constant E.1: Solve the Schr¨dinger equation for a constant potential V0 . The x equation is often called the Time Independent Schr¨dinger Equation. E is a constant.* o
6.1
Derivations and Computations
Linear Operators
Linear operators L satisfy the equation
. = E T (t)
Since we have a function of only x set equal to a function of only t.5
6.
h ψ(x.
2 −¯ 2 ∂ u(x) h 2m ∂x2
+ V (x)u(x) =
u(x)
i¯ ∂T (t) h ∂t = const.5. t) = u(x)e−iEt/¯
* See Example 6. The full time dependent solution is.
h T (t) = Ce−iEt/¯
and an equation in x set equal to a constant −¯ 2 ∂ 2 u(x) h + V (x)u(x) = E u(x) 2m ∂x2 which depends on the problem to be solved (through V (x)). In the equation above. ψ(x. o
−¯ 2 ∂ 2 u(x) h + V (x)u(x) = E u(x) 2m ∂x2
Here.6. (with some knowledge of the outcome). o −¯ 2 ∂ 2 u(x) h ∂T (t) + V (x)u(x) T (t) = i¯ u(x) h 2 2m ∂x ∂t Put everything that depends on x on the left and everything that depends on t on the right. We now have an equation in t set equal to a constant ∂T (t) i¯ h = E T (t) ∂t which has a simple general solution. t) = u(x)T (t) Plug this into the Schr¨dinger Equation.
t) is identiﬁed as the probability current. ∂P (x. t) = h ¯ ∂ψ ∂ψ ∗ − ψ ψ∗ 2mi ∂x ∂x
6.131
L(aψ + bφ) = aLψ + bLφ
where a and b are arbitrary constants and ψ and φ are arbitrary wavefunctions.6.
6. Diﬀerential operators clearly are linear also.6
6. We will ﬁnd two solutions for each energy E. t)ψ(x.1
Examples
Solution to the Schr¨dinger Equation in a Constant Potential o
Assume we want to solve the Schr¨dinger Equation in a region in which the potential is constant and o equal to V0 .
. A multiplicative constant is a simple linear operator. t) + =0 ∂t ∂x j(x. An example of a nonlinear operator (which we will not use) is N which has the property N ψ = ψ2 .5. ∂P (x. t) ∂ψ ∗ ∂ ∂ψ = (ψ ∗ (x. t) ∂j(x. t)) = ψ − ψ∗ ∂t ∂t ∂t ∂t Use the Schr¨dinger Equation o ∂ψ −¯ 2 ∂ 2 ψ h + V (x)ψ = i¯ h 2m ∂x2 ∂t and its complex conjugate ∂ψ ∗ −¯ 2 ∂ 2 ψ ∗ h . ∂P (x.)
Now we need to plug those equations in. Imaginary potentials do cause probability not to be conserved. + V (x)ψ ∗ = −i¯ h 2 2m ∂x ∂t (We assume V (x) is real.2
Probability Conservation Equation *
Start from the probability and diﬀerentiate with respect to time. t) 1 ¯ 2 ∂ 2 ψ∗ h −¯ 2 ∗ ∂ 2 ψ h = ψ ψ − V (x)ψ ∗ ψ + + V (x)ψ ∗ ψ ∂t i¯ 2m ∂x2 h 2m ∂x2 = 1 ¯ 2 ∂ 2 ψ∗ h ∂2ψ ∂ψ h ¯ ∂ ∂ψ ∗ ψ − ψ∗ ψ − ψ∗ 2 = 2 i¯ 2m ∂x h ∂x 2mi ∂x ∂x ∂x
This is the usual conservation equation if j(x.
Note that these are solutions for regions where the particle is not allowed classically. There are only two linearly independent solutions. but real exponentials. They will be useful to us for some solutions. −¯ 2 ∂ 2 ψ(x) h + V0 ψ(x) = Eψ(x) 2m ∂x2 ∂ 2 ψ(x) 2m = − 2 (E − V0 )ψ(x) 2 ∂x h ¯ Remember that x is an independent variable in the above equation while p and E are constants to be determined in the solution. We will use these solutions in Quantum Mechanics. there are solutions eikx and e−ikx
if we deﬁne k by the equation ¯ k = + 2m(E − V0 ). due to energy conservation. Lets write the solutions in terms of ¯ κ = i¯ k = 2m(V0 − E) The solutions are h h eκx and e−κx . We could also use the linear combinations of the above two solutions sin(kx) and cos(kx).
Sample Test Problems
. The solutions are also technically correct for E < V0 but k becomes imaginary. They are not deﬁnite momentum states.
These are not waves at all. The sin and cos solutions represent states of deﬁnite energy but contain particles moving to the left and to the right. 2. not both.132 We have the equation. For E > V0 . These are waves traveling in opposite directions h with the same energy (and magnitude of momentum).7
1. the total energy is less than the potential energy. We need to choose either the exponentials or the trig functions.
6.
∞
ψ=
i=1
αi ψi
. all the derivatives of ψ must go to zero at inﬁnity in order for the wave function to stay at zero. o H u(x) = E u(x) The Hamiltonian operates on u(x) the eigenfunction..
ψi ψj = δij
∞
ψ ∗ (x)ψ(x)dx = 1
−∞
We will assume that the eigenfunctions form a complete set so that any function can be written as a linear combination of them.1
Eigenfunctions. Solutions that are not normalizable must be discarded.133
7
7. there are many eigenfunction solutions (denoted here by the index i). times the same function. We will prove later that the eigenfunctions are orthogonal (See section 7.7. ψ = α1 ψ1 + α2 ψ2 + α3 ψ3 + . Eigenvalues and Vector Spaces
Eigenvalue Equations
The time independent Schr¨dinger Equation is an example of an Eigenvalue equation. A normalizable wave function must go to zero at inﬁnity. ψ(∞) → 0 In fact. giving a constant E the eigenvalue.. for bound states. (Eigen just means the same in German.
H ψi = Ei ψi
For states representing one particle (particularly bound states) we must require that the solutions be normalizable.1) to each other.) Usually.
134 (This can be proven for many of the eigenfunctions we will use.) Since the eigenfunctions are orthogonal, we can easily compute the coeﬃcients in the expansion of an arbitrary wave function ψ. αi = ψi ψ = ψi 
j
αj ψj =
j
ψi ψj αj =
j
δij αj = αi
We will later think of the eigenfunctions as unit vectors in a vector space (See section 7.4). The arbitrary wave function ψ is then a vector in that space. ⎞ α1 ⎜α ⎟ ψ =⎝ 2⎠ α3 ... It is instructive to compute the expectation value of the Hamiltonian using the expansion of ψ and the orthonormality of the eigenfunctions. ψHψ =
ij
⎛
αi ψi Hαj ψj =
ij
αi ψi αj Hψj α∗ αj Ej δij i
ij 2
=
ij
α∗ αj Ej ψi ψj = i α∗ αi Ei i
i
=
=
i
αi  Ei
We can see that the coeﬃcients of the eigenstates represent probability amplitudes to be in those states, since the absolute squares of the coeﬃcients α∗ αi obviously give the probability. i
7.2
Hermitian Conjugate of an Operator
First let us deﬁne the Hermitian Conjugate of an operator H to be H † . The meaning of this conjugate is given in the following equation.
∞
ψHψ =
−∞
ψ ∗ (x)Hψ(x)dx = ψHψ ≡ H † ψψ
That is, H † must operate on the conjugate of ψ and give the same result for the integral as when H operates on ψ. The deﬁnition of the Hermitian Conjugate of an operator can be simply written in BraKet notation.
A† φψ = φAψ
135 Starting from this deﬁnition, we can prove some simple things. Taking the complex conjugate ψA† φ = Aψφ Now taking the Hermitian conjugate of A† . A†
†
ψφ = Aψφ A†
†
=A
If we take the Hermitian conjugate twice, we get back to the same operator. Its easy to show that and (λA) = λ∗ A† (A + B) = A† + B †
† †
just from the properties of the dot product. We can also show that (AB)† = B † A† . φABψ = A† φBψ = B † A† φψ * See Example 7.8.1: Find the Hermitian conjugate of the operator a + ib.*
∂ ∂x .*
* See Example 7.8.2: Find the Hermitian conjugate of the operator
7.3
Hermitian Operators
A physical variable must have real expectation values (and eigenvalues). This implies that the operators representing physical variables have some special properties. By computing the complex conjugate of the expectation value of a physical variable, we can easily show that physical operators are their own Hermitian conjugate. ⎡ ∞ ⎤∗ ∞ ψHψ
∗
=⎣
−∞
ψ ∗ (x)Hψ(x)dx⎦ =
−∞
ψ(x)(Hψ(x))∗ dx = Hψψ
Hψψ = ψHψ = H † ψψ H† = H Operators that are their own Hermitian Conjugate are called Hermitian Operators.
H† = H
136
7.4
Eigenfunctions and Vector Space
Wavefunctions are analogous to vectors in 3D space. The unit vectors of our vector space are eigenstates. In normal 3D space, we represent a vector by its components.
3
r = xˆ + y y + z z = x ˆ ˆ
i=1
ri ui ˆ
The unit vectors ui are orthonormal, ˆ
ui · uj = δij ˆ ˆ
where δij is the usual Kroneker delta, equal to 1 if i = j and otherwise equal to zero. Eigenfunctions – the unit vectors of our space – are orthonormal. ψi ψj = δij We represent our wavefunctions – the vectors in our space – as linear combinations of the eigenstates (unit vectors).
∞
ψ=
i=1 ∞
αi ψi
φ=
j=1
βj ψj
In normal 3D space, we can compute the dot product between two vectors using the components. r1 · r2 = x1 x2 + y1 y2 + z1 z2 In our vector space, we deﬁne the dot product to be ψφ = αi ψi  βj ψj = α∗ βj i i=1 j=1 i=1 j=1 ∞ ∞ ∞ α∗ βj δij = α∗ βi i i i=1 j=1 i=1
∞ ∞ ∞ ∞
ψi ψj
=
We also can compute the dot product from the components of the vectors. Our vector space is a little bit diﬀerent because of the complex conjugate involved in the deﬁnition of our dot product. From a more mathematical point of view, the square integrable functions form a (vector) Hilbert Space. The scalar product is deﬁned as above.
∞
φψ =
−∞
d3 rφ∗ ψ
The properties of the scalar product are easy to derive from the integral. φψ = ψφ
∗
137 φλ1 ψ1 + λ2 ψ2 = λ1 φψ1 + λ2 φψ2 λ1 φ1 + λ2 φ2 ψ = λ∗ φ1 ψ + λ∗ φ2 ψ 1 2 ψψ is real and greater than 0. It equals zero iﬀ ψ = 0. We may also derive the Schwartz inequality. ψ1 ψ2 ≤ ψ1 ψ1 ψ2 ψ2
Linear operators take vectors in the space into other vectors. ψ = Aψ
7.5
The Particle in a 1D Box
As a simple example, we will solve the 1D Particle in a Box problem. That is a particle conﬁned to a region 0 < x < a. We can do this with the (unphysical) potential which is zero with in those limits and +∞ outside the limits. 0 0<x<a V (x) = ∞ elsewhere Because of the inﬁnite potential, this problem has very unusual boundary conditions. (Normally we will require continuity of the wave function and its ﬁrst derivative.) The wave function must be zero at x = 0 and x = a since it must be continuous and it is zero in the region of inﬁnite potential. The ﬁrst derivative does not need to be continuous at the boundary (unlike other problems), because of the inﬁnite discontinuity in the potential. The time independent Schr¨dinger equation (also called the energy eigenvalue equation) is o Huj = Ej uj with the Hamiltonian (inside the box) H=− Our solutions will have uj = 0 outside the box. The solution inside the box could be written as uj = eikx where k can be positive or negative. We do need to choose linear combinations that satisfy the boundary condition that uj (x = 0) = uj (x = a) = 0. We can do this easily by choosing uj = C sin(kx) which automatically satisﬁes the BC at 0. To satisfy the BC at x = a we need the argument of sine to be nπ there. nπx un = C sin a h ¯ 2 d2 2m dx2
138 Plugging this back into the Schr¨dinger equation, we get o −¯ 2 n2 π 2 h (− 2 )C sin(kx) = EC sin(kx). 2m a There will only be a solution which satisﬁes the BC for a quantized set of energies. En = h n2 π 2 ¯ 2 2ma2
We have solutions to the Schr¨dinger equation that satisfy the boundary conditions. Now we need to o set the constant C to normalize them to 1.
a
un un = C
2
2 0
sin2
nπx a dx = C2 a 2
Remember that the average value of sin is one half (over half periods). So we set C giving us the eigenfunctions nπx 2 sin un = a a The ﬁrst four eigenfunctions are graphed below. The ground state has the least curvature and the fewest zeros of the wavefunction.
Particle in a Box Eigenfunctions
n=1 n=2 n=3 n=4
u(x)
0
1 x
2
Note that these states would have a deﬁnite parity if x = 0 were at the center of the box. The expansion of an arbitrary wave function in these eigenfunctions is essentially our original Fourier Series. This is a good example of the energy eigenfunctions being orthogonal and covering the space.
139 7.5.1 The Same Problem with Parity Symmetry
If we simply redeﬁne the position of the box so that − a < x < a , then our problem has symmetry 2 2 under the Parity operation. x → −x The Hamiltonian remains unchanged if we make the above transformation. The Hamiltonian commutes with the Parity operator. [H, P ] = 0 This means that (P ui ) is an eigenfunction of H with the same energy eigenvalue. H(P ui ) = P (Hui ) = P Ei ui = Ei (P ui ) Thus, it must be a constant times the same energy eigenfunction. P ui = cui The equations says the energy eigenfunctions are also eigenfunctions of the parity operator. If we operate twice with parity, we get back to the original function, P 2 ui = ui so the parity eigenvalues must be ±1. P ui = ±1ui The boundary conditions are
a ψ(± ) = 0. 2
This gives two types of solutions. u+ (x) n u− (x) n
+ En − En
= = = =
2 cos a 2 sin a (2n − 1)2
(2n − 1)πx a 2nπx a
π2 ¯ 2 h 2ma2 π2 ¯ 2 h (2n)2 2ma2
Together, these are exactly equivalent to the set of solutions we had with the box deﬁned to be from 0 to a. The u+ (x) have eigenvalue +1 under the parity operator. The u− (x) have n n eigenvalue 1 under the parity operator. This is an example of a symmetry of the problem, causing an operator to commute with the Hamiltonian. We can then have simultaneous eigenfunctions of that operator and H. In this case all the energy eigenfunctions are also eigenstates of parity. Parity is conserved.
140 An arbitrary wave function can be written as a sum of the energy eigenfunctions recovering the Fourier series in its standard form.
∞
ψ(x) =
[A+ u+ (x) + A− u− (x)] n n n n
n=1
7.6
Momentum Eigenfunctions
We can also look at the eigenfunctions of the momentum operator. pop up (x) = pup (x) h ¯ d up (x) = pup (x) i dx The eigenstates are
h up (x) = Ceipx/¯
with p allowed to be positive or negative. These solutions do not go to zero at inﬁnity so they are not normalizable to one particle. pp = up up = ∞ This is a common problem for this type of state. We will use a diﬀerent type of normalization for the momentum eigenstates (and the position eigenstates).
∞
p p = C2
−∞
h ei(p−p )x/¯ dx = 2π¯ C2 δ(p − p ) h
Instead of the Kronecker delta, we use the Dirac delta function. The momentum eigenstates have a continuous range of eigenvalues so that they cannot be indexed like the energy eigenstates of a bound system. This means the Kronecker delta could not work anyway. These are the momentum eigenstates
1 h eipx/¯ up (x) = √ 2π¯ h
satisfying the normalization condition
p p = δ(p − p )
141 For a free particle Hamiltonian, both momentum and parity commute with H. So we can make simultaneous eigenfunctions. [H, p] = 0 [H, P ] = 0
We cannot make eigenfunctions of all three operators since [P, p] = 0. So we have the choice of the eikx states which are eigenfunctions of H and of p, but contain positive and negative parity components. or we have the sin(kx) and cos(kx) states which contain two momenta but are eigenstates of H and Parity. These are just diﬀerent linear combinations of the same solutions.
7.7
7.7.1
Derivations and Computations
Eigenfunctions of Hermitian Operators are Orthogonal
We wish to prove that eigenfunctions of Hermitian operators are orthogonal. In fact we will ﬁrst do this except in the case of equal eigenvalues. Assume we have a Hermitian operator A and two of its eigenfunctions such that Aψ1 = a1 ψ1 Aψ2 = a2 ψ2 .
Now we compute ψ2 Aψ1 two ways. ψ2 Aψ1 ψ2 Aψ1 = a1 ψ2 ψ1 = Aψ2 ψ1 = a2 ψ2 ψ1
Remember the eigenvalues are real so there’s no conjugation needed. Now we subtract the two equations. The left hand sides are the same so they give zero. 0 = (a2 − a1 ) ψ2 ψ1 If a1 = a2 then ψ2 ψ1 = 0. The eigenfunctions are orthogonal. What if two of the eigenfunctions have the same eigenvalue? Then, our proof doesn’t work. Assume ψ2 ψ1 is real, since we can always adjust a phase to make it so. Since any linear combination of ψ1
142 and ψ2 has the same eigenvalue, we can use any linear combination. Our aim will be to choose two linear combinations which are orthogonal. Lets try ψ+ ψ− = = 1 √ (ψ1 + ψ2 ) 2 1 √ (ψ1 − ψ2 ) 2
so ψ+ ψ− = = 1 (1 − 1 + ( ψ1 ψ2 − ψ2 ψ1 )) 2 1 ( ψ1 ψ2 − ψ2 ψ1 ) = 0. 2
This is zero under the assumption that the dot product is real. We have thus found an orthogonal set of eigenfunctions even in the case that some of the eigenvalues are equal (degenerate). From now on we will just assume that we are working with an orthogonal set of eigenfunctions.
7.7.2
Continuity of Wavefunctions and Derivatives
We can use the Schr¨dinger Equation to show that the ﬁrst derivative of the wave function o should be continuous, unless the potential is inﬁnite at the boundary. −¯ 2 d2 ψ h = (E − V (x))ψ 2m dx2 d2 ψ 2m = 2 (V (x) − E)ψ dx2 h ¯ Integrate both sides from just below a boundary (assumed to be at x = 0) to just above.
+
−
d2 ψ 2m dx = 2 dx2 h ¯
+
(V (x) − E)ψdx → 0
−
Let
go to zero and the right hand side must go to zero for ﬁnite potentials. dψ dx −
+
dψ dx
−
→0
Inﬁnite potentials are unphysical but often handy. The delta function potential is very handy, so we will derive a special continuity equation for it. Assume V (x) = V0 δ(x). Integrating the Schr¨dinger o Equation, we get
+
−
d2 ψ 2m dx = 2 dx2 h ¯
+
(V0 δ(x) − E)ψdx
−
143 As before, ﬁnite terms in the right hand integral go to zero as → 0, but now the delta function gives a ﬁxed contribution to the integral. dψ dx −
+
dψ dx
=
−
2m V0 ψ(0) h ¯2
There is a discontinuity in the derivative of the wave function proportional to the wave function at that point (and to the strength of the delta function potential).
7.8
7.8.1
Examples
Hermitian Conjugate of a Constant Operator
If we have the operator O = a + ib where a and b are real, what is its Hermitian conjugate? By the deﬁnition of the Hermitian conjugate φOψ = O† φψ . It is easy to see from the integral that (a − ib)φψ = φ(a + ib)ψ = (a + ib) φψ So the Hermitian conjugate of a constant operator is its complex conjugate.
7.8.2
Hermitian Conjugate of
∂ ∂x
∂ We wish to compute the Hermitian conjugate of the operator ∂x . We will use the integral to derive the result. ∞ ∂ ∂ψ(x) ψ = dx φ∗ (x) φ ∂x ∂x −∞
We can integrate this by parts, diﬀerentiating the φ and integrating to get ψ. ∂ φ ψ ∂x So the Hermitian conjugate of
∞
= [φ
∗
(x)ψ(x)]∞ −∞
−
−∞
∂φ∗ (x) ψ(x)dx = ∂x
−∂ φ ψ ∂x
∂ ∂x
∂ is − ∂x . h −∂ ¯ −i ∂x
Note that the Hermitian conjugate of the momentum operator is operator. So the momentum operator is Hermitian.
which is the same as the original
7.9
Sample Test Problems
1. A particle is conﬁned to a box of length L in one dimension. It is initially in the ground state. Suddenly, one wall of the box is moved outward making a new box of length 3L. What is the probability that the particle is in the ground state of the new box? You may ﬁnd it useful to know that sin(Ax) sin(Bx)dx = sin((A−B)x) − sin((A+B)x) 2(A−B) 2(A+B)
144 Answer P
(L) (3L) u0 u0
= =
 u0 u0
L
(L)
(3L) 2

L
πx 2 sin L L
0
πx 2 2 sin =√ 3L 3L 3L sin 4πx 3L 4π 2 3L =
L
sin
0
πx πx sin dx L 3L sin 1 4π 2π − sin 3 2 3
= = P =
2 √ − 3L √ √ √ 3 3 1− 3 − 2π 2 2 2 81 64π 2
sin 2πx 3L 2π 2 3L
0
2 3L = √ 3L 4π
9 8π
2. A particle of mass m is in a 1 dimensional box of length L. The particle is in the ground state. The size of the box is suddenly (symmetrically) expanded to length 3L. Find the probability for the particle to be in the ground state of the new potential. (Your answer may include an integral which you need not evaluate.) Find the probability to be in the ﬁrst excited state of the new potential. 3. Two degenerate eigenfunctions of the Hamiltonian are properly normalized and have the following properties. Hψ1 Hψ2 P ψ1 P ψ2 = = = = E0 ψ1 E0 ψ2 −ψ2 −ψ1
What are the properly normalized states that are eigenfunctions of H and P? What are their energies? 4. Find the ﬁrst (lowest) three Energy eigenstates for a particle localized in a box such that 0 < x < a. That is, the potential is zero inside the box and inﬁnite outside. State the boundary conditions and show that your solutions satisfy them. Normalize the solutions to represent one particle in the box. 5. A particle is in the ﬁrst excited state of a box of length L. What is that state? Now one wall of the box is suddenly moved outward so that the new box has length D. What is the probability for the particle to be in the ground state of the new box? What is the probability for the particle to be in the ﬁrst excited state of the new box? 6. * Assume that φ(p) = δ(p − p0 ). What is ψ(x)? What is < p2 >? What is < x2 >? 7. For a free particle, the Hamiltonian operator H is given by H = p2 /2m. Find the functions, op ψ(x), which are eigenfunction of both the Hamiltonian and of p. Write the eigenfunction that has energy eigenvalue E0 and momentum eigenvalue p0 . Now write the corresponding eigenfunctions in momentum space. 8. * A particle of mass m is in a 1 dimensional box of length L. The particle is in the ground state. A measurement is made of the particle’s momentum. Find the probability that the value measured is between p0 and p0 + dp.
Write down these two forms of the eigenfunctions of the Hamiltonian that are also eigenfunctions of these two operators. (Your answer may include an integral which you need not evaluate. A particle of mass m is in a constant potential V (x) = −V0 for all x.
. A particle is conﬁned to a ”box” in one dimension.) b) Assume that a particle is in the ground state of this box. The particle is in the ground state. That is the potential is zero for x between 0 and L. (Hint: Real functions will be simplest to use here. Now one wall of the box is suddenly moved from x = L to x = W where W > L. What is the probability that the particle is found in the ground state of the new potential? (You may leave your answer in the form containing a clearly speciﬁed integral. A particle of mass m is in a 1 dimensional box of length L. 10. and the potential is inﬁnite for x less than zero or x greater than L.145 9. These are the time independent solutions of this problem. there must be two ways to write the energy eigenfunctions. 12. one corresponding to each commuting operator. a) Give an expression for the eigenfunctions of the Hamiltonian operator. The size of the box is suddenly expanded to length 3L. Find the probability for the particle to be in the ground state of the new potential. What two operators commute with the Hamiltonian and can therefore be made constants of the motion? Since these two operators do not commute with each other.) Find the probability to be in the ﬁrst excited state of the new potential.) 11.
For simplicity.6. we will need these solutions in Quantum Mechanics.2
The Potential Step
We wish to study the physics of a potential step for the case E > V0 .1. The solutions are also technically correct for E < V0 but k becomes imaginary.1). V (x) = 0 +V0 x<0 x>0
. Note that these are solutions for regions where the particle is not allowed classically. due to energy conservation. Because of the multiple regions.
2m(E−V0 ) h2 ¯
positive and real. these problems will require more work with boundary conditions than is usual.1. We will ﬁnd solutions in each region of the potential. There are only two linearly independent solutions. but real exponentials. −¯ 2 d2 u(x) h + V0 u(x) = Eu(x) 2m dx2 d2 u(x) 2m(E − V0 ) =− u(x) dx2 h ¯2 For E > V0 .
8. We could also use the linear combination of the above two u(x) = A sin(kx) + B cos(kx)
We should use one set of solutions or the other in a region. Assume further that we are solving the time independent equation.146
8
8. lets write the solutions in terms of κ =
2m(V0 −E) . We must then match the solutions at the boundaries between the o regions.
8. the general solution is u(x) = Ae+ikx + Be−ikx with k = solutions. Nevertheless. These potentials have simple solutions to the Schr¨dinger equation. These are not waves at all.1
The General Solution for a Constant Potential
We have found the general solution of the Schr¨dinger Equation in a region in which the potential is o constant (See section 6. h2 ¯
which again is real and positive. the total energy is less than the potential energy.1
One Dimensional Potentials
Piecewise Constant Potentials in 1D
Several standard problems can be understood conceptually using two or three regions with constant potentials. not both. Assume the potential is equal to V0 and the total energy is equal to E. The general solution is
u(x) = Ae+κx + Be−κx .
) For x > 0 the solution is u (x) = T eik x k = 2m(E − V0 ) h ¯2
(Note that a beam coming from the right. since we have a beam with deﬁnite momentum. (Multiplying by some number does not change the physics. (A more physical problem to solve would use an incoming wave packet with a spread in momentum. The exponentials are all equal to 1 there so the equation is simple.) Continuity of the wave function at x = 0 implies 1 + R = T. For x < 0.)
Energy e ikx E V0
incident wave reflected transmitted
ikx + Re
Te ik’x V(x)
0 0 x
There are two unknown coeﬃcients R and T which will be determined by matching boundary conditions. We will not require normalization to one particle. so we will use the complex exponential solutions in both regions. This is essentially a 1D scattering problem. would have given a e−ik x term for x > 0. h ¯2
Note we have assumed the coeﬃcient of the incident beam is 1.
. which cannot be so normalized. Assume there is a beam of particles with deﬁnite momentum coming in from the left and assume there is no ﬂux of particles coming from the right.147 For this problem. the solution is u(x) = eikx + Re−ikx k= 2mE . both regions have E > V .
The transmission probability goes to 0 for k = 0 (since the kinetic energy is zero). all with E > V .7.) If we wish to compute the transmission probability. (k + k )2
We’ll get the same answers for the reﬂection and transmission coeﬃcients using the probability ﬂux (See section 8. continuing on to inﬁnity. In Quantum Mechanics.1. the easy way to do it is to say that its Ptransmission = 1 − Preﬂection = 4kk . all of the particles would be transmitted.148 Continuity of the derivative of the wavefunction at x = 0 gives [ikeikx − ikRe−ikx ]x=0 = [ik T eik x ]x=0 Evaluate and plug in T from the equation above. k+k R=
We now have the full solution.3
The Potential Well with E > 0 *
With positive energy.1) to solve the problem. Preﬂection = R2 = k−k k+k
2
(Note that we can simply use the coeﬃcient of e−ikx because the incoming term has a coeﬃcient of 1 and because the reﬂected particles are moving with the same velocity as the incoming beam. We can solve the problem. u(x) = eikx +
k−k −ikx k+k e 2k ik x k+k e
x<0 x>0
Classically. now with three regions of the potential. ⎧ x < −a ⎨ 0 V (x) = −V0 −a < x < a ⎩ 0 x>a
. The transmission probability goes to 1 one k = k (since there is no step). some probability is reﬂected.
8. this is again a scattering type problem. k(1 − R) = k (1 + R) (k + k )R = (k − k )
The coeﬃcients are k−k k+k 2k T =1+R = . given our assumption of particles incident from the left.
149 Numbering the three regions from left to right. u1 (x) = eikx + Re−ikx u2 (x) = Aeik x + Be−ik x u3 (x) = T eikx
Again we have assumed a beam of deﬁnite momentum incident from the left and no wave incident from the right. classically. Quantum mechanically.
ik’x Aeik’x + Be ikx eikx + Re
Energy
Teikx E x
reflected
transmitted
0
incident wave
V0 0
V(x)
There are four unknown coeﬃcients. We now match the wave function and its ﬁrst derivative at the two boundaries yielding 4 equations. there is a probability to be transmitted and a probability to be reﬂected. = e−2ika 2kk cos(2k a) − i(k 2 + k 2 ) sin(2k a)
The squares of these give the reﬂection and transmission probability.7. everything would be transmitted because the energy is larger than the potential. The reﬂection probability will go to zero for certain energies: R → 0 if 2k a = nπ
. since the potential is the same in the two regions.2) R T = ie−2ika (k 2 − k 2 ) sin(2k a) 2kk cos(2k a) − i(k 2 + k 2 ) sin(2k a) 2kk . Some hard work yields reﬂection and transmission amplitudes (See section 8. Again.
electrons scattering oﬀ atoms may have nearly zero cross section at some particular energy.
. The scattering cross section often goes to zero for certain particular energies.
8. making this a bound state problem. h ¯2
The e−κx term will not be acceptable at −∞ and the eκx term will not be acceptable at +∞ since they diverge and we could never normalize to one bound particle. u1 (x) u3 (x) = = C1 eκx C3 e−κx
In the center we’ll use the sine and cosine solutions anticipating parity eigenstates.1.150
k =
2m(E − V0 ) h ¯2 n2 π 2 ¯ 2 h 8ma2
E = −V0 +
There are analogs of this in 3D. In the left and right regions the general solution is u(x) = Aeκx + Be−κx with κ= −2mE . For example.4
Bound States in a Potential Well *
We will work with the same potential well as in the previous section but assume that −V0 < E < 0. Again this is a wave property. u2 (x) = A cos(kx) + B sin(kx) k= 2m(E + V0 ) h ¯2
Again we will have 4 equations in 4 unknown coeﬃcients. Note that this potential has a Parity symmetry.
In the graph shown. The even states have the (quantization) constraint on the energy that κ = tan(ka)k
⎛ −2mE = tan ⎝ h ¯2
⎞
2m(E + V0 ) ⎠ 2m(E + V0 ) a h ¯2 h ¯2 ⎛ ⎞ −E 2m(E + V0 ) ⎠ = tan ⎝ a E + V0 h ¯2
and the odd states have the constraint κ = − cot(ka)k ⎞ 2m(E + V0 ) ⎠ a h ¯2
⎛ −E = − cot ⎝ E + V0
These are transcendental equations. Where the curves intersect (not including the asymptote). the more solutions.7. there are 2 even and one odd solution. so we will solve them graphically. This means that the solutions separate into even parity and odd parity states. The wider and deeper the well. The plot below compares the square root on the left hand side of the transcendental equations to the tangent on the right for the event states and to “cotangent” on the right for odd states. We could have guessed this from the potential.151
Energy C1eκx
ikx Aeikx + Be
0
C3e
−κx
x E
V0 0
V(x)
The calculation (See section 8.3) shows that either A or B must be zero for a solution. There is always one even solution for the 1D potential well. is an allowed energy.
.
It allows you to vary the potential and see the eigenstates. For the solutions outside the barrier. u1 (x) = eikx + Re−ikx u2 (x) = Aeκx + Be−κx u3 (x) = T eikx x < −a −a < x < a x>a
Again we assume a beam of deﬁnite momentum incident from the left and no wave incident from the right. h ¯2
. k= 2mE . ⎧ ⎨ 0 V (x) = +V0 ⎩ 0 Numbering the three regions from left to right.5
The Potential Barrier
With an analysis of the Potential Barrier problem.152
Potential Well Bound States
5 4 3 2 1 0 1 2 3 4 5 20
sqrt tan "cot"
f(E)
15
10 E (hbar**2/2ma**2)
5
0
Try this 1D Potential Applet.
8.1. we can understand the phenomenon of quantum tunneling.
T 2 = (2kκ)2 → (k 2 + κ2 )2 sinh2 (2κa) + (2kκ)2 4kκ 2 + κ2 k
2
e−4κa
An approximate probability is sometimes useful. semiconductors.
a
T  ≈ e
2
−2κ(2a)
−2
=e
−a
2m [V h2 ¯
(x)−E]
dx
Classically the transmission probability would be zero.
. the particle is allowed to violate energy conservation for a short time and so has a chance to tunnel through the barrier. h ¯2
Energy Aeκx +Be−κx V(x)
e
ikx
+ Re
ikx
Te ikx
transmitted
reflected incident wave
V0
E 0 x
0
This is actually the same as the (unbound) potential well problem with the substitution k → iκ in the center region.153 Inside the barrier. Tunneling can be applied to cold emission of electrons from a metal. alpha decay of nuclei. and many other problems. The amplitude to be transmitted is T = e−2ika 2kκ . In Quantum Mechanics. 2kκ cosh(2κa) − i(k 2 − κ2 ) sinh(2κa)
We can compute the probability to be transmitted. κ= 2m(V0 − E) .
7. then multiply that solution by a polynomial. k ω= m The Harmonic Oscillator Hamiltonian becomes. show that the polynomial series must terminate if the solutions are to be normalizable. It is standard to remove the spring constant k from the Hamiltonian. derive a recursion relation between the coeﬃcients of the polynomial. 2m dx2 2 To solve the Harmonic Oscillator equation (See section 8.4).154
8. The potential is unphysical because it does not go to zero at inﬁnity. and this potential can be solved exactly. Many potentials look like a harmonic oscillator near their minimum. 2m dx2 2 Note that this potential also has a Parity symmetry. then ﬁnd the form of the solution for x → ±∞. we will ﬁrst change to dimensionless variables. derive the energy eigenvalues. it is often a very good approximation. however. The energy eigenvalues are
En =
n+
1 2
h ¯ω
. o The harmonic oscillator Hamiltonian is given by H= p2 1 + kx2 2m 2
which makes the Schr¨dinger Equation for energy eigenstates o −¯ 2 d2 u 1 2 h + kx u = Eu.2
The 1D Harmonic Oscillator
The harmonic oscillator is an extremely important physics problem. then ﬁnally derive the functions that are solutions. This is the ﬁrst nonconstant potential for which we will solve the Schr¨dinger Equation. replacing it with the classical oscillator frequency.
H=
1 p2 + mω 2 x2 2m 2
The diﬀerential equation to be solved is −¯ 2 d2 u 1 h + mω 2 x2 u = Eu.
u2 (x) = C 1 − 2
mωx2 h ¯
e−mωx
2
/2¯ h
Note that n is equal to the number of zeros of the wavefunction. The general solution can be written as
∞
un (x) =
k=0
ak y k e−y
2
/2
with the coeﬃcients determined by the recursion relation
ak+2 =
2(k − n) ak (k + 1)(k + 2)
and the dimensionless variable y given by.. With more zeros. the solutions either have even or odd parity.
. The ground state wave function is.
u0 (x) =
mω π¯ h
1 4
e−mωx
2
/2¯ h
This is a Gaussian (minimum uncertainty) distribution. with a ﬁrst order polynomial multiplying the same Gaussian. The ﬁrst excited state is an odd parity state..
u1 (x) =
mω π¯ h
1 4
2mω −mωx2 /2¯ h xe h ¯
The second excited state is even parity.. 2.155 for n = 0. with a second order polynomial multiplying the same Gaussian. There are a countably inﬁnite number of solutions with equal energy spacing. a wavefunction has more curvature and hence more kinetic energy. Since the HO potential has a parity symmetry. The ground state is even parity. We have been forced to have quantized energies by the requirement that the wave functions be normalizable. This is a common trend. 1. .
156
y=
mω x h ¯
The series terminates with the last nonzero term having k = n. A. V (x) = −aV0 δ(x) These will have energy less than zero so the solutions are ψ(x) = where Aeκx Ae−κx x<0 x>0
−2mE .3
The Delta Function Potential *
Take a simple. h ¯2 There are only two regions. We don’t need to worry about the one point at x = 0 – the two solutions will match there. above and below the delta function.
8. for the solution in both regions. κ=
Energy
e 0 E
κx
e−κx 0 x
V(x)
. We have already made the wave function continuous at x = 0 by using the same coeﬃcient. attractive delta function potential and look for the bound states.
5) 2maV0 = 1 + tanh(κd) κ¯ 2 h This is a transcendental equation.7. to some extent. the boundary conditions at −d are the same as at d. Recall that the delta function causes a known discontinuity in the ﬁrst derivative (See section 7. For even parity. The boundary conditions determine the constant A and constrain κ. −2mE m2 a2 V02 = h ¯2 h ¯4 ma2 V02 E=− 2¯ 2 h
There is only one energy for which we can satisfy the boundary conditions. There is only one bound state in an attractive delta function potential.7. so we can assume that our solutions will be parity eigenstates.4
The Delta Function Model of a Molecule *
The use of two delta functions allows us to see. how atoms bind into molecules. κ= A little calculation gives (See section 8. Our potential is V (x) = −aV0 (δ(x + d) + δ(x − d)) with attractive delta functions at x = ±d. h ¯2 Since the solution is designed to be symmetric about x = 0. our solution in the three regions is ⎧ x < −d eκx ⎨ κx ψ(x) = A (e + e−κx ) −d < x < d ⎩ e−κx x>d −2mE .2).157 We now need to meet the boundary condition on the ﬁrst derivative at x = 0. but we can limit the energy. This is a parity symmetric potential. dψ dx −
+
dψ dx
2maV0 ψ(0) h ¯2 − 2maV0 −κ − κ = − h ¯2 maV0 κ= h ¯2 =−
Putting in the formula for κ in terms of the energy. 2maV0 <2 κ¯ 2 h maV0 κ> h ¯2
.
8.
74 Angstroms.5 eV. Emolecule < Eatom Basically. The ﬁgure below shows the two solutions plotted on the same graph as the potential. This state would be called antibonding. κ¯ 2 h 2maV0 >2 κ¯ 2 h maV0 κ< h ¯2 This energy is larger than for one delta function. This allows the kinetic energy to be lower.
1D Molecule
4
2
0
2
V(x) 4 u0(x) u1(x)
u(x)
x
Two Hydrogen atoms bind together to form a molecule with a separation of 0. If we approximate the Coulomb potential by with a delta function.6) eV Angstroms. this κ = −2mE is larger than the one for the single delta h2 ¯ h2 ¯ function. setting aV0 = (0.158 Since κ = maV0 for the single delta function. which is at least the right order of magnitude. The odd parity solution has an energy that satisﬁes the equation 2maV0 = 1 + coth(κd). our very naive calculation would give 1. The binding energy (for the two electrons) is about 4. just larger than the Bohr radius of 0. the electron doesn’t have to be a localized with two atoms as it does with just one.53 Angstroms.48 eV for one electron.
.53)(2)(13. This means that E is more negative and there is more binding energy.
maV0 sin(ka) h ¯ 2k
cos(φ) = cos(ka) +
Since cos(φ) can only take on values between 1 and 1. This potential has a new symmetry. that a translation by the lattice spacing a leaves the problem unchanged. If this is not between 1 and 1. that value of k and the corresponding energy are not allowed.6) similar to the quantized energies for bound states.
∞
V (x) = aV0
n=−∞
δ(x − na)
Our states will have positive energy. there are allowed bands of k and gaps between those bands. The probability distributions must therefore have this symmetry ψ(x + a)2 = ψ(x)2 .
. which means that the wave function diﬀers by a phase at most.7. The graph below shows cos(ka) + maV0 sin(ka) as a function of k. we derive a constraint on k (See section 8. ψ(x + a) = eiφ ψ(x)
The general solution in the region (n − 1)a < x < na is ψn (x) = An sin(k[x − na]) + Bn cos(k[x − na])
k=
2mE h ¯2
By matching the boundary conditions and requiring that the probability be periodic.159
8. there h2 k ¯ is no solution.5
The Delta Function Model of a Crystal *
The KronigPenny model of a solid crystal contains an inﬁnite array of repulsive delta functions.
Solids with partially ﬁlled bands are conductors. Solids
.160
Energy Bands
2
1 cos(phi) cos(phi) E
0
1
2 0 5 k (/A) 10
This energy band phenomenon is found in solids.
Lets just go ahead and write our wavefunction. the 3 components of angular momentum do not commute with each other.6
The Quantum Rotor
It is useful to simply investigate angular momentum with just one free rotation angle. This might be the quantum plane propeller. Semiconductors have a small number of charge carriers (or holes) in a band.
h h ei(px−Et)/¯ = ei(prφ−Et)/¯ h Remembering angular momentum. so there is no potential. h This will prove to be true for 3 dimensions too. I am back to x = 0. 2.. lets call the combination pr = L.
The angular momentum must be quantized in units of ¯ . ψ∗ 2mi ∂x ∂x
We can save some eﬀort by noticing that this contains an expression minus its complex conjugate. however. then x = rφ and the one problem we have is that once I go completely around the circle. The kinetic energy is 1 mv 2 = 2m for p = mr dφ . We will do a good job of this in 3 dimensions later.
8. 3.
8. t) = ∂ψ ∂ψ ∗ h ¯ − ψ .7. leading to all kinds of fun.1
Derivations and Computations
Probability Flux for the Potential Step *
The probability ﬂux is given by j(x.
This must be single valued so we need to require that
h h ei(2πL−Et)/¯ = ei(0−Et)/¯ h ei(2πL)/¯ = 1
L = n¯ h n = 0.) j= h ¯ h ¯ du du∗ du − u = − CC u∗ u∗ 2im dx dx 2im dx
. (This assures that term in brackets is imaginary and the ﬂux is then real. Lets assume we have a mass m constrained to move in a circle of radius r.7
8. Assume the motion p2 in the circle is free.161 with ﬁlled bands are insulators. 2 dt If we measure distance around the circle. Our wave is ei(Lφ−Et)/¯ .. 1.
T eika = Aeik a + Be−ik a ikT eika = ik Aeik a − ik Be−ik a k ika T e = Aeik a − Be−ik a k 1 k Aeik a = T eika 1 + 2 k 1 k Be−ik a = T eika 1 − 2 k
. At x = a we have 2 equations which we can use to eliminate A and B. u1 (x) = eikx + Re−ikx u2 (x) = Aeik x + Be−ik x u3 (x) = T eikx
Again we have assumed no wave incident from the right (but we could add that solution if we wanted).2
Scattering from a 1D Potential Well * ⎧ ⎨ 0 V (x) = −V0 ⎩ 0
x < −a −a < x < a x>a
Numbering the three regions from left to right. T 2 again as we had calculated earlier. j = T 2 m The probability to be transmitted is the transmitted ﬂux divided by the incident ﬂux. In this case its easy to see that its R2 as we said. That’s good since we have 4 constants to determine. For x > 0 h ¯k . We now match the wave function and its ﬁrst derivative at the two boundaries yielding 4 equations. 4k 2 k 4kk h ¯k m = = m ¯k h (k + k )2 k (k + k )2
8.162 For x < 0 j j j = = = h ¯ [(e−ikx + R∗ eikx )(ikeikx − ikRe−ikx ) − CC] 2im i¯ k h [1 − Re−2ikx + R∗ e2ikx − R∗ R] + CC 2im h ¯k [1 − R2 ] . m
The probability to be reﬂected is the reﬂected ﬂux divided by the incident ﬂux.7.
e−ika + Reika = e−ika − Reika 2e−ika = 1 ika Te 2 1 ika Te 2 1 = T eika 2 k + 2+ k 1+ k k e−2ik a + 1 − k k e2ik a
4e−2ika
k k + 1 e−2ik a − − 1 e2ik a k k k k k − e−2ik a + 2 − e2ik a k k k k k = T 4 cos(2k a) − 2i + sin(2k a) k k T = T = 2e−2ika k 2 cos(2k a) − i k +
−2ika k k
sin(2k a)
2kk e 2kk cos(2k a) − i (k 2 + k 2 ) sin(2k a)
We can subtract the same equations to most easily solve for R. e−ika + Reika = Ae−ik a + Beik a ike−ika − ikReika = ik Ae−ik a − ik Beik a 1 k k e−ika + Reika = T eika 1 + e−2ik a + 1 − e2ik a 2 k k 1 k k ke−ika − kReika = T eika k 1+ e−2ik a − 1 − e2ik a 2 k k 1 k k + 1 e−2ik a − − 1 e2ik a e−ika − Reika = T eika 2 k k We can add equations to eliminate R.163 At x = −a we have 2 equations which can now be written in terms of R and T by using the above. = e−2ika 2kk cos(2k a) − i(k 2 + k 2 ) sin(2k a) = ie−2ika
. 2Reika = 1 ika Te 2 k k k k e2ik a − e−2ik a + − k k k k k k 1 R = T −2i sin(2k a) + 2i sin(2k a) 4 k k k i k R = T sin(2k a) − 2 k k ikk e−2ika sin(2k a) R= R=
k k
−
k k
2kk cos(2k a) − i (k 2 + k 2 ) sin(2k a) i k 2 − k 2 sin(2k a)e−2ika 2kk cos(2k a) − i (k 2 + k 2 ) sin(2k a)
We have solved the boundary condition equations to ﬁnd the reﬂection and transmission amplitudes R T (k 2 − k 2 ) sin(2k a) 2kk cos(2k a) − i(k 2 + k 2 ) sin(2k a) 2kk .
Divide these two pairs of equations to get two expressions for κ.) We will have 4 equations in 4 unknown coeﬃcients. we have two expressions for the same quantity.164 The squares of these give the reﬂection and transmission probability. κ −κ = = kA sin(ka) + kB cos(ka) A cos(ka) − B sin(ka) −kA sin(ka) + kB cos(ka) A cos(ka) + B sin(ka)
Factoring out the k. since the potential is the same in the two regions.
At a we get C3 e−κa = A cos(ka) + B sin(ka) −κC3 e−κa = −kA sin(ka) + kB cos(ka). h ¯2
In the center we have the same solution as before. κ A sin(ka) + B cos(ka) = k A cos(ka) − B sin(ka) A sin(ka) − B cos(ka) κ = k A cos(ka) + B sin(ka)
. u2 (x) = A cos(kx) + B sin(kx) k= 2m(E + V0 ) h ¯2
(Note that we have switched from k to k for economy.3
Bound States of a 1D Potential Well *
In the two outer regions we have solutions u1 (x) = C1 eκx u3 (x) = C3 e−κx κ= −2mE .7.
8. At −a we get C1 e−κa = A cos(ka) − B sin(ka) κC1 e−κa = kA sin(ka) + kB cos(ka).
7. y= mω x h ¯
. A sin(ka) + B cos(ka) A sin(ka) − B cos(ka) = A cos(ka) − B sin(ka) A cos(ka) + B sin(ka) and cross multiply. but not both. the even states have the constraint on the energy that κ = tan(ka)k and. the odd states have the constraint κ = − cot(ka)k. κ= A sin(ka) + B cos(ka) k A cos(ka) − B sin(ka)
k If we set B = 0. We have parity eigenstates. −¯ 2 d2 u 1 h + mω 2 x2 u = Eu.165 If we equate the two expressions. What’s left is AB(sin2 (ka) + cos2 (ka)) AB = AB(− cos2 (ka) − sin2 (ka)) = −AB
Either A or B. 2m dx2 2 By working with dimensionless variables and constants. we have (A sin(ka) + B cos(ka))(A cos(ka) + B sin(ka)) = (A cos(ka) − B sin(ka))(A sin(ka) − B cos(ka)). Now lets use one equation. we can see the basic equation and minimize the clutter. We use the energy in terms of ¯ ω.4
Solving the HO Diﬀerential Equation *
The diﬀerential equation for the 1D Harmonic Oscillator is. derived from the solutions and boundary conditions.
The A2 and B 2 terms show up on both sides of the equation and cancel. This means that the states separate into even parity and odd parity states. must be zero. h 2E = h ¯ω We deﬁne a dimensionless coordinate.
8. if we set A = 0. We could have guessed this from the potential. again.
2E h ¯ d2 u + mω dx2 h ¯ω 2 d u 2m + 2 (E − dx2 h ¯ It works. Take the diﬀerential equation d2 u + ( − y 2 )u = 0 dy 2 and plug u(y) = h(y)e−y into it to get
2 2 2 d2 h(y)e−y /2 + h(y)e−y /2 − y 2 h(y)e−y /2 = 0 dy 2 2 2 d2 h(y) −y2 /2 dh(y) −y2 /2 e −2 − h(y)e−y /2 + h(y)y 2 e−y /2 ye dy 2 dy 2 2
/2
/2
+ h(y)e−y
2
2
/2
− y 2 h(y)e−y
2
/2
=0
d h(y) dh(y) − h(y) + y 2 h(y) + h(y) − y 2 h(y) = 0 − 2y dy 2 dy dh(y) d2 h(y) + ( − 1)h(y) = 0 − 2y dy 2 dy
.) Now we want to ﬁnd the solution for y → ∞. d2 u 2m 1 + 2 (E − mω 2 x2 )u = 0 dx2 2 h ¯ d2 u + ( − y 2 )u = 0 dy 2
(Its probably easiest to just check the above equation by substituting as below.
This exponential will dominate a polynomial as y → ∞ so we can write our general solution as u(y) = h(y)e−y where h(y) is a polynomial. d2 u + ( − y 2 )u = 0 dy 2 becomes d2 u − y2u = 0 dy 2 u = e−y
2
−
mω 2 x h ¯
=0
1 mω 2 x2 )u = 0 2
which has the solution (in the large y limit)
/2
.166 The equation becomes.
am+2 = 2m + 1 − 2 am → am (m + 1)(m + 2) m
The series for
y 2 ey has the coeﬃcient of y 2n+2 equal to
1 2n n!
y 2n+2 2n n! and the coeﬃcient of y 2n equal to
2
/2
=
1 2n−1 (n−1)! .
∞
[am (m)(m − 1)y m−2 − 2am (m)y m + ( − 1)am y m ] = 0
m=0
We now want ot shift terms in the sum so that we see the coeﬃcient of y m . we will shift the term am (m)(m − 1)y m−2 down two steps in the sum. am+2 = The series will terminate if = 2n + 1 2m + 1 − am (m + 1)(m + 2)
.) We must avoid this. each coeﬃcient of y m must be zero. But. To do this. 2n m
2
So our polynomial solution will approach y 2 ey /2 and our overall solution will not be normalizable. For large m. We can avoid the problem if the series terminates and does not go on to inﬁnite m. 2 (Remember u(y) = h(y)e−y /2 . h(y) =
m=0 ∞
am y m
Plug it into the diﬀerential equation. This is OK since am (m)(m − 1)y m−2 is zero for m = 0 or m = 1. Write h(y) as a sum of terms. lets see what we have.
∞
[am+2 (m + 2)(m + 1) − 2am (m) + ( − 1)am ]y m = 0
m=0
(Note that in doing this shift the ﬁrst term for m = 0 and for m = 1 get shifted out of the sum.
If m = 2n.167 This is our diﬀerential equation for the polynomial h(y).
am+2 =
1 1 am = am . It will now show up as am+2 (m + 2)(m + 1)y m .) For the sum to be zero for all y. am+2 (m + 2)(m + 1) + ( − 1 − 2m)am = 0 Solve for am+2 am+2 =
2m + 1 − am (m + 1)(m + 2)
and we have a recursion relation giving us our polynomial.
∞
−y2 2
= a0 e−mωx
2
/2¯ h
a0 2 e−mωx
−∞
2
/¯ h
dy = 1
a0 2 u0 (x) = mω π¯ h
1 4
π¯ h =1 mω e−2mωx
2
/¯ h
8. The boundary conditions determine the constant A and constrain κ. Then the last term in the series will be of order n. the boundary conditions at −d are the same as at d. we get quantized energies when we satisfy the boundary conditions at inﬁnity.5
1D Model of a Molecule Derivation * ⎧ ⎨ ψ(x) =
eκx A (eκx + e−κx ) ⎩ e−κx κ= −2mE . e−κd = A eκd + e−κd A= e−κd eκd + e−κd
. h ¯2
x < −d −d < x < d x>d
Since the solution is designed to be symmetric about x = 0. The ground state wavefunction is particularly simple. having only one term.168 for some value of n.7. an+2 = 0 an = 0 (n + 1)(n + 2)
The acceptable solutions then satisfy the requirement 2E = 2n + 1 h ¯ω (2n + 1) 1 E= h ¯ω = n + h ¯ω 2 2 = Again. u0 (x) = a0 e Lets ﬁnd a0 by normalizing the wavefunction. Continuity of ψ gives.
Bn+1 = cos(ka)
.169 The discontinuity in the ﬁrst derivative of ψ at x = d is −κe−κd − Aκ eκd − e−κd = − 2maV0 −κd e h ¯2 eκd − e−κd 2maV0 −1 − A =− e−κd κ¯ 2 h κd −κd e −e 2maV0 −1 − κd =− e + e−κd κ¯ 2 h κd 2maV0 e − e−κd = 1 + κd 2 e + e−κd κ¯ h 2maV0 = 1 + tanh(κd) κ¯ 2 h
We’ll need to study this transcendental equation to see what the allowed energies are.
Our states have positive energy.7. This potential has the symmetry that a translation by the lattice spacing a leaves the problem unchanged.
8. ψ(x + a) = eiφ ψ(x) The general solution in the region (n − 1)a < x < na is ψn (x) = An sin(k[x − na]) + Bn cos(k[x − na]) k = sqrt 2mE h ¯2
Now lets look at the boundary conditions at x = na. which means that the wave function diﬀers by a phase at most.6
1D Model of a Crystal Derivation *
We are working with the periodic potential
∞
V (x) = aV0
n=−∞
δ(x − na). Continuity of the wave function gives ψn (na) = ψn+1 (na) An sin(0) + Bn cos(0) = An+1 sin(−ka) + Bn+1 cos(−ka) Bn = −An+1 sin(ka) + Bn+1 cos(ka) Bn + An+1 sin(ka) . The probability distributions must therefore have this symmetry ψ(x + a)2 = ψ(x)2 .
An+1 Bn+1 An+1 Bn+1 = = = = 2maV0 Bn cos(ka) − Bn sin(ka) + An cos(ka) h ¯ 2k 2maV0 Bn sin(ka) + Bn cos(ka) + An sin(ka) h ¯ 2k eiφ An eiφ Bn
Using the second pair of equations to eliminate the n + 1 coeﬃcients.170 The discontinuity in the ﬁrst derivative is 2maV0 ψn (na) h ¯2 na na 2maV0 k[An+1 cos(−ka) − Bn+1 sin(−ka)] − k[An cos(0) − Bn sin(0)] = Bn h ¯2 2maV0 k[An+1 cos(ka) + Bn+1 sin(ka) − An ] = Bn h ¯2 − = dψn+1 dx dψn dx
Substituting Bn+1 from the ﬁrst equation 2maV0 Bn h ¯2 2maV0 An+1 (cos(ka) + sin(ka) tan(ka)) + Bn tan(ka) − An = Bn h ¯2k cos2 (ka) + sin2 (ka) 2maV0 An+1 = Bn − Bn tan(ka) + An cos(ka) h ¯ 2k 2maV0 An+1 = Bn cos(ka) − Bn sin(ka) + An cos(ka) h ¯ 2k k[An+1 cos(ka) + [Bn + An+1 sin(ka)] tan(ka) − An ] =
Plugging this equation for An+1 back into the equation above for Bn+1 we get Bn+1 Bn+1 Bn+1 Bn+1 Bn+1 = = = = = Bn + An+1 sin(ka) cos(ka) Bn +
2maV0 Bn h2 k ¯
cos(ka) − Bn sin(ka) + An cos(ka) sin(ka) cos(ka)
2maV0 Bn sin2 (ka) + + An sin(ka) Bn sin(ka) − Bn 2 cos(ka) cos(ka) h ¯ k 2maV0 1 Bn + − cos(ka) + An sin(ka) Bn sin(ka) − Bn cos(ka) cos(ka) h ¯ 2k 2maV0 Bn sin(ka) + Bn cos(ka) + An sin(ka). we have (eiφ − cos(ka))An = 2maV0 cos(ka) − sin(ka) Bn h ¯ 2k
. h ¯ 2k
We now have two pairs of equations for the n + 1 coeﬃcients in terms of the n coeﬃcients.
there are allowed bands of k and gaps between those bands. Calculate the probability to be transmitted. Since cos(φ) can only take on values between 1 and 1. h ¯ 2k
eiφ − cos(ka) −
Now we can eliminate all the coeﬃcients. Assume V0 is a positive real number. Answer −2mE h ¯2
κ=
.
8.8
Examples
This whole section is examples. Get a numerical answer.9
Sample Test Problems
1. (Don’t assume that V0 has the units of energy.171 2maV0 sin(ka) Bn = sin(ka)An . (eiφ − cos(ka))(eiφ − cos(ka) − = e2iφ − eiφ 2maV0 sin(ka)) h ¯2k
e2iφ − eiφ Multiply by e−iφ . A beam of 100 eV (kinetic energy) electrons is incident upon a potential step of height V0 = 10 eV.
8. like the constraints that give us quantized energies for bound states. 2.) You need not normalize the state. * Find the energy eigenstates (and energy eigenvalues) of a particle of mass m bound in the 1D potential V (x) = −V0 δ(x).
2maV0 cos(ka) − sin(ka) sin(ka) h ¯ 2k 2maV0 sin(ka) + cos(ka) + cos(ka) h ¯ 2k 2maV0 + 2 sin(ka) cos(ka) + cos2 (ka) h ¯ k 2maV0 sin(ka) cos(ka) − sin2 (ka) = h ¯2k 2maV0 sin(ka) + 2 cos(ka) + 1 = 0 h ¯ 2k
eiφ + e−iφ −
2maV0 sin(ka) + 2 cos(ka) = 0 h ¯ 2k maV0 cos(φ) = cos(ka) + 2 sin(ka) h ¯ k
This relation puts constraints on k.
* A beam of particles of energy E > 0 coming from −∞ is incident upon a delta function potential in one dimension. * A beam of particles of wavenumber k (this means eikx ) is incident upon a one dimensional potential V (x) = aδ(x). c) Find h(y) for the ground state and second excited state. Answer To the left of the origin the solution is eikx + Re−ikx . h2 ¯
Transmission probability starts at zero for k = 0 then approaches P = 1 asymptotically for k >
4. Calculate the probability to be transmitted. o b) Determine the coeﬃcients needed to satisfy the boundary conditions. Continuity of ψ at the origin implies 1 + R = T .
b) Use the requirement that this polynomial series must terminate to ﬁnd the allowed energies in terms of α. To the right of the origin the solution is T eikx . c) Calculate the probability for a particle in the beam to be reﬂected by the potential and the probability to be transmitted. dx h ¯ 2ma ikT − (ik − ikR) = 2 T h ¯ 2ma 2ik(T − 1) = 2 T h ¯ 2ma T = 2ik 2ik − 2 h ¯ 2ik T = 2ik + 2ma h2 ¯ Δ PT = T 2 = 4k 2 2 2 4k 2 + 4m 4a h ¯
ma .172 −2mV0 κ0 e h ¯2 + − −2mV0 −κ − (+κ) = h ¯2 mV0 κ= 2 h ¯ h ¯ 2 m2 V02 h ¯ 2 κ2 mV02 =− E=− = 2m 2m ¯ 4 h 2¯ 2 h du dx − du dx = 3. The discontinuity in the ﬁrst derivative is 2ma dψ = 2 ψ(0). * The Schr¨dinger equation for the one dimensional harmonic ocillator is reduced to the following o equation for the polynomial h(y): d2 h(y) E dh(y) + ( − 1)h(y) = 0 − 2y 2 dy dy α
∞
a) Assume h(y) =
m=0
am y m and ﬁnd the recursion relation for the coeﬃcients am . a) Find the solution to the Schr¨dinger equation for this problem. Graph it as a function of k. 5. That is V (x) = λδ(x).
.
) of a harmonic oscillator potential.
b) Use the requirement that this polynomial series must terminate to ﬁnd the allowed energies in terms of α. * A particle is in the ground state (ψ(x) = ( mω ) 4 e 2¯ . o b) Determine the coeﬃcients needed to satisfy the boundary conditions. Assume that the wave function of the particle is unchanged by removing the potential. but do not evaluate. * Find the energy eigenstates (and energy eigenvalues) of a particle of mass m bound in the 1D potential V (x) = −λδ(x). up to a normalization factor. c) Find h(y) for the ground state and second excited state. That is V (x) = 0 for x < 0 and V (x) = −V0 for x > 0 where V0 is a positive real number. c) Calculate the probability for a particle in the beam to be reﬂected by the potential step and the probability to be transmitted. 9. A beam of particles of energy E > 0 coming from −∞ is incident upon a potential step in one dimension. * The Schr¨dinger equation for the one dimensional harmonic oscillator is reduced to the following o equation for the polynomial h(y): E dh(y) d2 h(y) + ( − 1)h(y) = 0 − 2y dy 2 dy α
∞
a) Assume h(y) =
m=0
am y m and ﬁnd the recursion relation for the coeﬃcients am . 11. π¯ h Suddenly the potential is removed without aﬀecting the particle’s state.173 6.
.
h 7. a) Calculate this energy eigenfunction. You need not evaluate the integral. from the recursion relations given on the front of the exam. 1 −mωx2
8. Find the probability distribution P (p) for the particle’s momentum after the potential has been removed. * A particle is in the third excited state (n=3) of the one dimensional harmonic oscillator potential. c) At t = 0 the potential is suddenly removed so that the particle is free. a) Find the solution to the Schr¨dinger equation for this problem. Write an expression for the probability that the particle has momentum in the range (p. p + dp) for t > 0. 10. b) Give. the expression for the normalization factor.
3) for Harmonic Oscillator states √ n + 1un+1
A† un =
and that A is a lowering operator. A† ] = 1
The commutators with the Hamiltonian are easily computed.
[A. A ]
†
= −¯ ωA h = hωA† ¯
From these commutators we can show that A† is a raising operator (See section 9. A† and H to solve the HO problem. A] [H.174
9
Harmonic Oscillator Solution using Operators
Operator methods are very useful both for solving the Harmonic Oscillator problem and for any type of computation for the HO potential. The operators we develop will also be useful in quantizing the electromagnetic ﬁeld.
H = hω A† A + ¯
1 2
We will use the commutators (See section 9.1)
A≡
p mω x + i√ 2¯ h 2m¯ ω h
and its Hermitian conjugate A† . It can be rewritten in terms of the operator A (See section 9. [H.
.2) between A. The Hamiltonian for the 1D Harmonic Oscillator H= 1 p2 + mω 2 x2 2m 2
looks like it could be written as the square of a operator.
First just compute the quantity A† A = i mω 2 p2 x + + (xp − px) 2¯ h 2m¯ ω 2¯ h h
. but often it is more useful to deﬁne the nth eigenstate in terms of the ground state and raising operators.5) can be deduced by using the diﬀerential operators for A and A† . Note that A is chosen so that A† A is close to the Hamiltonian.175
Aun =
√
nun−1
Because the lowering must stop at a ground state with positive energy.1
Introducing A and A†
The Hamiltonian for the 1D Harmonic Oscillator H= can be rewritten in terms of the operator A A≡ and its Hermitian conjugate A† = p mω x − i√ 2¯ h 2m¯ ω h p mω x + i√ 2¯ h 2m¯ ω h 1 p2 + mω 2 x2 2m 2
Both terms in the Harmonic Oscillator Hamiltonian are squares of operators.
1 un = √ (A† )n u0 n!
Almost any calculation of interest can be done without actual functions since we can express the operators for position and momentum. 2 The actual wavefunctions (See section 9. x = p = h ¯ (A + A† ) 2mω m¯ ω h (A − A† ) −i 2
9. we can show that the allowed energies are 1 En = n + h ¯ ω.
This is easy if H is written in terms of A and A† . A† ] = hωA† ¯ ¯ ¯
9. x] 2¯ h 2m¯ ω h 2¯ h 2¯ h i i (−[x. A† and H
We will use the commutator between A and A† to solve the HO problem. p] + [p. x] + [p. A ]
†
= −¯ ωA h = hωA† ¯
. p] + [p. p] − [x. A] = hω[A† . The operators are deﬁned to be A A† = = p mω x + i√ 2¯ h 2m¯ ω h p mω x − i√ 2¯ h 2m¯ ω h . A† ] = hωA† [A. A† ] = = 1 i i mω [x. [H. x] = 1. x] 2¯ h 2m¯ ω 2¯ h h 1 p2 1 + mω 2 x2 − ¯ ω. H = hω A† A + ¯ 1 2 . A] [H.3
Use Commutators to Derive HO Energies
We have computed the commutators [H.176 i mω 2 p2 x + − [p. 2¯ h h ¯
Lets use this simple commutator [A.
9. A† ] = 1 to compute commutators with the Hamiltonian. A] = [H. h 2m 2 2
A† A = h ¯ ω(A† A) =
From this we can see that the Hamiltonian can be written in terms of A† A and some constants.2
Commutators of A. x]) = [p. A† ] = hω[A† A. A]A = −¯ ωA ¯ ¯ h hω[A† A.
The commutator is [A.
apply [H. [H. 1 1 p ψp ψ + mω 2 x ψx ψ ≥ 0 2m 2 The only way to stop the lowering operator from taking the energy negative. h Now. [H. Therefore. A† ] to the energy eigenfunction un . ψHψ = Au0 = 0 Since the Hamiltonian contains A in a convenient place. we can deduce the ground state energy. When we lower the ground state.177 Apply [H.
It is interesting to note that we have a number operator for n H Nop H = = = A† A + A† A 1 h (Nop + )¯ ω 2 1 2 h ¯ω
. is for the lowering to give zero for the wave function.A lowers the energy by ¯ ω. A† ]un = hωA† un ¯ † † HA un − A Hun = hωA† un ¯ H(A† un ) − En (A† un ) = hω(A† un ) ¯ † ¯ H(A un ) = (En + hω)(A† un ) ¯ h A† un is an eigenfunction of H with eigenvalue En + hω. A]un = −¯ ωAun h HAun − AHun = −¯ ωAun h H(Aun ) − En (Aun ) = −¯ ωAun h H(Aun ) = (En − ¯ ω)(Aun ) h h This equation shows that Aun is an eigenfunction of H with eigenvalue En − ¯ ω. A† raises the energy by ¯ ω. 1 1 h ¯ Hu0 = hω(A† A + )u0 = ¯ ωu0 2 2 The ground state energy is E0 = 1 ¯ ω and the states in general have energies 2h E= n+ 1 2 h ¯ω
since we have shown raising and lowering in steps of ¯ ω. Only a state with energy E0 = 1 ¯ ω can stop h 2h the lowering so the only energies allowed are E= n+ 1 2 h ¯ ω. We cannot keep lowering the energy because the HO energy cannot go below zero. we must get zero. A] to the energy eigenfunction un . this must happen for the ground state. Because this will be at the lowest energy.
1 un = √ (A† )n u0 n!
9.6. C2 = = A† un A† un = AA† un un (A† A + [A.6.6.
Similarly.* h 2
.*
n + ¯ ω.4
Expectation Values of p and x
It is important to realize that we can just use the deﬁnition of A to write x and p in terms of the raising and lowering operators.6. x = p = h ¯ (A + A† ) 2mω m¯ ω h (A − A† ) −i 2
This will allow for any computation.3: 9.* 1 2 2 2 mω x for any energy eigenstate is
p2 2m 1 2
1 2
n+
1 2
1 2
h ¯ ω. the eﬀect of the lowering operator is Aun = √ nun−1 .2: 9.* p for any energy eigenstate is zero.5: The expectation value of * See Example 9.1: 9.1 Raising and Lowering Constants
We know that A† raises the energy of an eigenstate but we do not know what coeﬃcient it produces in front of the new state.6.
These are extremely important equations for any computation in the HO problem.4: The The The The expectation expectation expectation expectation value value value value of of of of x for any energy eigenstate is zero. * * * * See See See See Example Example Example Example 9.* 1 x in the state √2 (u0 + u1 ).6: The expectation value of p as a function of time for the state ψ(t = 0) = √ 1 √ (u1 + u2 ) is − m¯ ω sin(ωt).6.* h for any energy eigenstate is * See Example 9. A† un = Cun+1 We can compute the coeﬃcient using our operators.178 9. A† ])un un = (n + 1) un un = n + 1
The eﬀect of the raising operator is A† un = √ n + 1un+1 .3. We can also write any energy eigenstate in terms of the ground state and the raising operator.
Write A in terms of x and p and try it.5
The Wavefunction for the HO Ground State
The equation Au0 = 0 can be used to ﬁnd the ground state wavefunction.
We could continue with the raising operator to get excited states. the dot product with the original (orthogonal) state must give zero.
9. Since each term in the x operator changes the eigenstate.) The expectation value of p also gives zero. un pun = −i m¯ ω h un A − A† un = 0 2
.6.6.1
Examples
The expectation value of x in eigenstate
We can compute the expectation value of x simply. u0 = Ce−mωx
2
/2¯ h
.2
The expectation value of p in eigenstate
(See the previous example is you want to see all the steps.
9. p mω x + i√ u0 = 0 2¯ h 2m¯ ω h d mωx + h ¯ u0 = 0 dx du0 mωx =− u0 dx h ¯ This ﬁrst order diﬀerential equation can be solved to get the wavefunction.6
9. un xun = = h ¯ h ¯ un A + A† un = ( un Aun + un A† un ) 2mω 2mω √ h ¯ √ ( n un un−1 + n + 1 un un+1 ) = 0 2mω
We should have seen that coming. √ 1u1 = mω x− 2¯ h h ¯ d 2mω dx u0
Usually we will not need the actual wave functions for our calculations.179
9.
1 u0 + u1 x u0 + u1 2
= = = = + + = =
h ¯ u0 + u1 A + A† u0 + u1 2mω h ¯ u0 + u1 Au0 + Au1 + A† u0 + A† u1 8mω √ √ √ h ¯ u0 + u1 0 + 1u0 + 1u1 + 2u2 8mω √ h ¯ √ ( 1 u0 u0 + 1 u0 u1 8mω √ √ 2 u0 u2 + 1 u1 u0 √ √ 1 u1 u1 + 2 u1 u2 ) h ¯ (1 + 1) 8mω h ¯ 2mω
1 2
9.180 9. 1 1 1 un  mω 2 x2 un = mω 2 n + 2 2 2 h ¯ 1 = mω 2 n+ 1 2 h ¯ω = 1 En 2
. un x2 un = = = √ √ h ¯ ( un  n + 1Aun+1 + un  nA† un−1 ) 2mω √ √ √ √ h ¯ ( un  n + 1 n + 1un + un  n nun ) 2mω h ¯ 1 h ¯ ((n + 1) + n) = n + 2mω 2 mω
With this we can compute the expected value of the potential energy.3 The expectation value of x in the state
1 √ (u0 2
+ u1 ).4
The expectation value of
1 2 2 2 mω x
in eigenstate
The expectation of x2 will have some nonzero terms.6. un x2 un = = h ¯ un AA + AA† + A† A + A† A† un 2mω h ¯ un AA† + A† Aun 2mω
We could drop the AA term and the A† A† term since they will produce 0 when the dot product is taken.6.
3 5 3 1 1 ψ(t) = √ (u1 e−i 2 ωt + u2 e−i 2 ωt ) = √ e−i 2 ωt (u1 + e−iωt u2 ) 2 2
We can compute the expectation value of p.)
9. Answer 2 u0 − i 3 1 u1 3
. A 1D harmonic oscillator is in a linear combination of the energy eigenstates ψ= Find the expected value of p.6
Time Development Example
Start oﬀ in the state at t = 0.6. e−iEt/¯ .181
p2 2m
9. ψpψ m¯ ω 1 h u1 + e−iωt u2 A − A† u1 + e−iωt u2 2 2 m¯ ω 1 h u1 Au2 e−iωt − u2 A† u1 eiωt = 2 2i m¯ ω 1 √ −iωt √ iωt h = 2e − 2e 2 2i √ = − m¯ ω sin(ωt) h = −i
9.6. 1 ψ(t = 0) = √ (u1 + u2 ) 2
h Now put in the simple time dependence of the energy eigenstates.7
Sample Test Problems
1.5
The expectation value of
p2 2m
in eigenstate
The expectation value of
is p2 un 2m = = = h −1 m¯ ω un  − AA† − A† Aun 2m 2 h ¯ω un AA† + A† Aun 4 1 h ¯ω ((n + 1) + n) = En 4 2
un 
(See the previous section for a more detailed computation of the same kind.
What is the product ΔpΔx? Answer Its easy to see that x = 0 either from the integral or using operators. calculate un pum . I’ll use operators to compute ¯ the rest. Use the commutator relation between A and A† to derive [H. Assuming un represents the nth 1D harmonic oscillator energy eigenstate. Similarly. evaluate the uncertainty in p for the ground state. Now show that A is the lowering operator for the harmonic oscillator energy. Answer m¯ ω A − A† h 2 i m¯ ω h un A − A† um = −i 2 √ m¯ ω √ h ( mδn(m−1) − m + 1δn(m+1) ) = −i 2
p un pum
=
3.182
ψpψ
=
−i −i −i −
m¯ ω h 2 m¯ ω h 2 m¯ ω h (−i 2 8 9
2 u0 − i 3 2 u0 − i 3
1 u1 A − A†  3 1 u1  − 3
2 u0 − i 3 1 u0 3
1 u1 3
= = =
2 u1 − i 3
2 2 −i ) 9 9 2√ m¯ ω h = m¯ ω h 2 3
2. Evaluate the “uncertainty” in x for the 1D HO ground state u0 (x − x)2 u0 where x = ¯ ¯ u0 xu0 .
. x u0 x2 u0 = = = p u0 p2 u0 Δx Δp ΔpΔx = = = = = h ¯ (A + A† ) 2mω h ¯ u0 AA + AA† + A† A + A† A† )u0 2mω h ¯ h ¯ h ¯ u0 AA† u0 = 1= 2mω 2mω 2mω 1 m¯ ω h (A − A† ) i 2 m¯ ω h m¯ ω h u0  − AA† u0 = − 2 2 h ¯ 2mω m¯ ω h 2 h ¯ 2
4. A].
a one dimensional harmonic oscillator is in the state ψ(t = 0) = Calculate the expected value of p as a function of time.
6. At t = 0. a harmonic oscillator is in a linear combination of the n = 1 and n = 2 states. 3 2 u1 − 3 1 u2 3
. At t = 0. 2 u0 + 3 1 u2 .
3 4 u0 + i
1 4 u1 . ψ= Find x and x2 as a function of time. 7. A 1D harmonic oscillator is in a linear combination of the energy eigenstates ψ= Find x2 .183
5. 8.
ABψ = A(Bψ ) = (AB)ψ An operator transforms one vector into another vector. a · b ≤ a b the magnitude of the dot product is limited by the magnitude of the vectors.1
More Fun with Operators
Operators in a Vector Space
Review of Operators
First.1.
. Operators are associative but not commutative.184
10
10. ψφ ≤ This is called the Schwartz inequality. much like the familiar 3D vector space. r = av1 + bv2 in 3D space becomes ψ = λ1 ψ1 + λ2 ψ2 . The scalar product is deﬁned as
∞
φψ =
−∞
dx φ∗ (x)ψ(x)
and many of its properties can be easily deduced from the integral. φ = Oφ Eigenfunctions of Hermitian operators Hi = Ei i form an orthonormal ij = δij complete set ψ =
i ∗
= ψφ
ψψ φφ
iψ i =
i
i iψ . φψ As in 3D space.1
10. Recall that the square integrable functions form a vector space. a little review.
if we sum over a complete set of states. giving the coeﬃcient of j in the state. h ψ(t) = iψ(0) i e−iEi t/¯
i
The basis of deﬁnite momentum states is not in the vector space. then its multiplied by the unit vector j . The sum of the projection operators is 1. φψ =
i
b ∗ ci i
The expansion in energy eigenfunctions is a very nice way to do the time development of a wave function.1. Expanding the vectors φ and ψ .
i i = 1
i
. so this is an operator.2
Projection Operators j j and Completeness
Now we move on a little with our understanding of operators. as in 3D space. with the right length to be a projection. An operator maps one vector into another vector. A ket vector followed by a bra vector is an example of an operator.185 Note that we can simply describe the j th eigenstate at j . φ ψ =
i
bi i ci i
i
=
we can take the dot product by multiplying the components. ci = iψ ψ(x) = xψ φ(p) = pψ
10. For example the operator which projects a vector onto the j th eigenstate is j j First the bra vector dots into the state. 1 ψ = √ 2π¯ h
∞
dpφ(p)p
−∞
Any of these amplitudes can be used to deﬁne the state. yet we can use this basis to form any state in the vector space. like the eigenstates of a Hermitian operator. turning it back into a vector.
We could already see this in the decomposition of ψ above.1. φψ = U φU ψ = φU † U ψ This means that U † U = 1.186 This is an extremely useful identity for solving problems. (the vector displacement between the proton and the electron). and two angular momentum quantum numbers to describe Hydrogen states. py and pz to describe that state.2
A Complete Set of Mutually Commuting Operators
If an operator commutes with H. This is an important tool both for solving the problem and for labeling the eigenfunctions.
10. The Hydrogen atom also has 3 coordinates for the position of the atom. P =
subspace
i i
We could use this to project out the odd parity states. We will need three quantum numbers to describe the state.
∞
p p dp = 1
−∞
We can form a projection operator into a subspace.
.
10. Usually. The will allow us to change from one orthonormal basis to another. The operators commute with each other. We will use an energy index. for example.
Unitary operators will be important for the matrix representation of operators. A complete set of mutually commuting operators will allow us to deﬁne a state in terms of the quantum numbers of those operators. we can make simultaneous eigenfunctions of energy and that operator. The operators will all commute with each other. ψ =
i
The same is true for deﬁnite momentum states. For example. We will might use px .3
Unitary Operators
Unitary operators preserve a scalar product. i iψ . the Hydrogen atom in three dimensions has 3 coordinates for the internal problem. we will need one quantum number for each degree of freedom in the problem.
the Mean Square uncertainty in the physical quantity represented is deﬁned as (ΔA)2 (ΔB)2 = = ψ(A − A )2 ψ = ψU 2 ψ ψ(B − B )2 ψ = ψV 2 ψ
where we deﬁne (just to keep our expressions small) U V = A − ψAψ = B − ψBψ . V ]ψ = 0 −i ψ[U. V ]ψ ≥ 0 Choose a λ to minimize the expression.
10. ∂ =0 ∂λ 2λ(ΔB)2 + i ψ[U. First. The dot product must be greater than or equal to zero. notice that [U. (ΔA)2 + λ2 (ΔB)2 + iλ ψ[U. Now we will dot U ψ + iλV ψ into itself to get some information about the uncertainties. so lets identify them. If we also add the spin of the proton to the problem. V ]ψ 2 + ≥0 4 (ΔB)2 2(ΔB)2 1 i (ΔA)2 (ΔB)2 ≥ − ψ[U. so much for the deﬁnitions. U ψ + iλV ψU ψ + iλV ψ ≥ 0 ψU ψ + λ ψV ψ + iλ U ψV ψ − iλ V ψU ψ ≥ 0
2 2 2
This expression contains the uncertainties. the we need still one more quantum number to describe the state. V ]ψ λ= 2(ΔB)2
Plug in that λ. to get the strongest inequality. identifying the commuting operators to be used before solving the problem will usually save time.187 If we also consider the spin of the electron in the Hydrogen atom.
Since A and B are just constants. V ]ψ 2 = ψ [U. given a state ψ. If it is possible. V ] = [A.3
Uncertainty Principle for NonCommuting Operators
Let us now derive the uncertainty relation for noncommuting operators A and B. V ]ψ 2 4 2 (ΔA)2 −
. 1 ψ[U. we ﬁnd that we need to add one more commuting operator to label the states and to compute the energies accurately. B] OK. V ]ψ 2 ψ[U.
as in the case of [p. this agrees with the uncertainty principle we know.V ]2 V )ψ 2(ΔB) into itself and require that its positive. this has three terms. A] ψ + ψ ψ h ¯ ∂t
This is an important general result for the time derivative of expectation values. B] 2
If the commutator is a constant. the expectation values can be removed. x] = 2 2
(Note that we could have simpliﬁed the proof by just stating that we choose to dot (U + i [U.
(Δp)(Δx) ≥
h ¯ i [p. B] 2
For momentum and position. It would not have been clear that this was the strongest condition we could get. (ΔA)(ΔB) ≥ i [A. A] ψ dt h ¯
.
(ΔA)(ΔB) ≥
i [A. Thinking about the integral.4
Time Derivative of Expectation Values *
We wish to compute the time derivative of the expectation value of an operator A in the state ψ. x]. d ψ A ψ dt = = = dψ dψ ∂A A ψ + ψ ψ + ψ A dt ∂t dt 1 −1 ∂A Hψ A ψ + ψ A Hψ + ψ ψ i¯ h i¯ h ∂t i ∂A ψ [H. A] ψ + ψ dt h ¯ ∂t
which becomes simple if the operator itself does not explicitly depend on time. i d ψ A ψ = ψ [H.
∂A i d ψ ψ A ψ = ψ [H.)
10.188 This result is the uncertainty for noncommuting operators.
5
The Time Development Operator *
We can actually make an operator that does the time development of a wave function. p] = dt h ¯ h ¯
V (x). In some cases.
h e−iHt/¯ is the time development operator.
h ¯ d i dx
=−
dV (x) dx
which Mr. This is called the Ehrenfest Theorem. We can apply this to verify that the expectation value of x behaves as we would expect for a classical particle.
i i dp = [H. x] = dt h ¯ h ¯
p2 .x 2m
=
p m
This is a good result. We can expand this exponential to understand its meaning a bit. Newton told us a long time ago. o i¯ h ∂ψ = Hψ ∂t
h ψ(t) = e−iHt/¯ ψ(0)
where H is the operator. It takes a state from time 0 to time t.
10.189 Expectation values of operators that commute with the Hamiltonian are constants of the motion. it can be easily computed.
.
i i d x = [H. For momentum.
h e−iHt/¯ =
(−iHt/¯ )n h n! n=0
∞
This is an inﬁnite series containing all powers of the Hamiltonian. We just make the simple exponential solution to the Schr¨dinger equation using operators.
A(t) = e−iωt A(0) A† (t) = eiωt A† (0)
We can combine these to get the momentum and position operators in the Heisenberg picture. Take the Hermitian conjugate. B]e−iHt/¯ = [H. [H. We can then deﬁne the operator that depends on time. ψ(t)Bψ(t) = =
h h e−iHt/¯ ψ(0)Be−iHt/¯ ψ(0) h h ψ(0)eiHt/¯ Be−iHt/¯ ψ(0)
According to our rules. In it.
h h B(t) = eiHt/¯ Be−iHt/¯
If we use this operator. the operators evolve with time and the wavefunctions remain constant. The usual Schr¨dinger picture has the states evolving and the operators constant. A] = −¯ ωA h i dA = − ¯ ωA = −iωA h dt h ¯ We can integrate this. lets compute the expectation value of an operator B.6
The Heisenberg Picture *
To begin. As an example. B(t)] h ¯ h ¯
It is governed by the commutator with the Hamiltonian. We have already computed the commutator. we may look at the HO operators A and A† . p(t) = x(t) = p(0) cos(ωt) − mωx(0) sin(ωt) p(0) sin(ωt) x(0) cos(ωt) + mω
. we can multiply operators together before using them. d B(t) dt = = iH iHt/¯ −iHt/¯ h h h iH −iHt/¯ h e e Be − eiHt/¯ B h ¯ h ¯ i iHt/¯ i h h e [H. we don’t need to do the time development of the wavefunctions! This is called the Heisenberg Picture. o We can now compute the time derivative of an operator.190
10.
Calculate the commutator [Lx . y]px h ¯ h h (−xpz + zpx ) = i¯ (xpz − zpx ) = −i¯ Ly i i i h ¯ [Lx . ψxψ = = = = 1 2 1 2 1 2 h ¯ u1 + eiωt u2 A + A† u1 + eiωt u2 2mω h ¯ u1 Au2 e−iωt + u2 A† u1 eiωt 2mω √ −iωt √ iωt h ¯ 2e + 2e 2mω h ¯ cos(ωt) mω
In the Heisenberg picture ψx(t)ψ = 1 2 h ¯ ψe−iωt A + eiωt A† ψ 2mω
This gives the same answer with about the same amount of work. State the uncertainty principle for Lx and Lz . py ]pz + z[py .
1 ψ(t = 0) = √ (u1 + u2 ) 2
In the Schr¨dinger picture. Lz ] = = ΔLx ΔLz ≥
2.
10. o
3 5 3 1 1 ψ(t) = √ (u1 e−i 2 ωt + u2 e−i 2 ωt ) = √ e−i 2 ωt (u1 + e−iωt u2 ) 2 2
We can compute the expectation value of x.7
10.1
Examples
Time Development Example
Start oﬀ in the state.8
Sample Test Problems
1. Answer [ypz − zpy . Calculate the rate of change of x p the expected values of x and p. Lz ] = (−i¯ ) Ly = Ly h 2 2 2
[Lx .7. xpy − ypx ] = x[y. * A particle of mass m is in a 1 dimensional potential V (x). ( ddt and ddt ). Your answer will obviously depend on the state
.191
10. Lz ] where Lx = ypz − zpy and Lz = xpy − ypx .
Answer dA dt dx dt 1 [A. c) Compute < ui P ui > the mean momentum in the state ui >. V (x)] i¯ h i¯ i dx h dV − dx
= = =
dp dt
= =
3. H n ] ]= n! n! n=0 n=0
∞
∞
∞
n(it)n [A. H] i¯ h 1 p2 x. * Assume that the states ui > are the eigenstates of the Hamiltonian with eigenvalues Ei .
∞
(it)n H n (it)n [A.
+ u1 ). Compute the commutators [A† . A]An−1 = −nAn−1 [A.192 of the particle and on the potential. 5. eiHt ] for the 1D harmonic oscillator. a particle of mass m is in the Harmonic Oscillator state ψ(t = 0) = the Heisenberg picture to ﬁnd the expected value of x as a function of time. * At t = 0.X] where X is the position operator. i¯ h 2m p −¯ h 1 p = i¯ m h i m 1 1 ¯ d h [p. the Hamiltonian is given by H = Compute the commutator [H. An ] = [A. V (x)] = [ . An ] and [A.
1 √ (u0 2 p2 2m
+ V (x). eiHt ] = = it (it)n−1 ¯ ωAH n−1 h (n − 1)! n=1
∞
n[A† . A]ui >= 0 for an arbitrary linear operator A. (Hui >= Ei ui >). H]H n−1 (it)n−1 ¯ ωAH n−1 h = it n! (n − 1)! n=0 n=1 it¯ ωA h it¯ ωA h (it)n−1 H n−1 (n − 1)! n=1 (it)n H n = it¯ ωAeiHt h (n)! n=0
∞ ∞
= =
4. Use
. Answer [A† . a) Prove that < ui [H. b) For a particle of mass m moving in 1dimension.
p2 ] = [x2 .
. The momentum is a constant of the motion. ∂x1 ∂x2
We can write the derivatives in terms of the total momentum operator. [x1 . The original Schr¨dinger equation o Hψ(x1 . p2 ] = [x1 . H= p2 p2 1 + 2 + V (x1 . Momentum is conserved. x2 )dx h ¯ h ¯
Subtract of the initial Schr¨dinger equation and commute E through p. Lets examine an inﬁnitesimal translation in x. the potential will only depend on the diﬀerence in the positions of the two particles. x2 ) = Eψ(x1 . x2 ) = Ep ψ(x1 . x2 )dx = Eψ(x1 . The Hamiltonian for two particles can be easily written. x2 ] = [p1 . x2 ) 2m1 2m2
Often. o Hp ψ(x1 . x2 ) +
i i Hp ψ(x1 . x2 + dx) = Eψ(x1 + dx. x2 ) transforms to Hψ(x1 + dx. x2 ) + ∂ψ ∂ψ dx + dx . There may be an interaction between the two particles in the potential. V (x1 . x2 ) + Ep ψ(x1 . x2 ) We have proven that [H. We can have simultaneous eigenfunctions of the total momentum and of energy. p1 ] = 0
The kinetic energy terms in the Hamiltonian are independent. p = p1 + p2 = h ¯ i ∂ ∂ + ∂x1 ∂x2
Hψ(x1 .1
Extending QM to Two Particles and Three Dimensions
Quantum Mechanics for Two Particles
We can know the state of two particles at the same time. The positions and momenta of particle 2 commute with the positions and momenta of particle 1. x2 ) + ∂ψ ∂ψ dx + dx ∂x1 ∂x2 = E ψ(x1 . p] = 0 if the Hamiltonian has translational symmetry. x2 ) = V (x1 − x2 ) This means that the overall Hamiltonian has a translational symmetry. x2 ) = pHψ(x1 . x2 + dx) which can be Taylor expanded H ψ(x1 .193
11
11.
∇1 = ∇r + m1 ∇R m1 + m2
.
r ≡ r1 − r2
We also deﬁne the vector position of the center of mass.2
Quantum Mechanics in Three Dimensions
We have generalized Quantum Mechanics to include more than one particle. The fact that the commutators are zero can be calculated from the operators that we know. 2m 2m 2m 2m 2m
This extension is really very simple. ∂R ∂ d ∂r ∂ + = dr1 ∂r1 ∂r ∂r1 ∂R In three dimensions we would have. We now wish to include more than one dimension too. Additional dimensions are essentially independent although they may be coupled through the potential. For example. py ] = [x. As a simple example. The Hamiltonian in 3D is H= p2 p2 p2 h ¯2 2 p2 y x + + z + V (r) = + V (r) = − ∇ + V (r).
R≡
m1 r1 + m2 r2 m1 + m2
We will use the chain rule to transform our Hamiltonian. H= p2 p2 1 + 2 + V (r1 − r2 ) 2m 2m
We deﬁne the vector diﬀerence between the coordinates of the particles. if we were working in one dimension we might use the chain rule like this. The coordinates and momenta from diﬀerent dimensions commute. [x.3
Two Particles in Three Dimensions
The generalization of the Hamiltonian to three dimensions is simple.194
11.
11. h ¯ ∂ ] = 0. i ∂y
The kinetic energy can simply be added and the potential now depends on 3 coordinates.
H =−
h ¯2 2 h ¯2 2 ∇r − ∇ + V (r) 2μ 2M R
The Hamiltonian actually separates into two problems: the motion of the center of mass as a free particle −¯ 2 2 h ∇ H= 2M R and the interaction between the two particles.
.
H =−
h ¯2 2 ∇ + V (r) 2μ r
This is exactly the same separation that we would make in classical physics. 2(m1 + m2 )2 R
1 1 1 = + μ m1 m2
and the total mass
M = m1 + m2
we get.195 ∇2 = −∇r + Putting this into the Hamiltonian we get H= −¯ 2 h ∇2 + r 2m1 m1 m1 + m2
2 2
m2 ∇R m1 + m2
∇2 + R
2m1 ∇r · ∇R m1 + m2
+
−¯ 2 h ∇2 + r 2m2
m2 m1 + m2
∇2 − R ∇2 + r
2m2 ∇r · ∇R + V (r) m1 + m2
H = −¯ 2 h Deﬁning the reduced mass μ
1 1 + 2m1 2m2
m1 + m2 ∇2 + V (r).
This is often called the Pauli exclusion principle.) Thus. It is also related to the fact that fermions can only be created in conjunction with antifermions. Some particles. Hence. x2 ) so the possible eigenvalues of the interchange operator are just +1 and 1. They are identical in every way. If we interchange twice. no two fermions can be in the same state.5
Sample Test Problems
1. x2 ) = ψ(x2 . The overall wavefunction changes sign whenever we interchange any pair of fermions. Answer The energy levels are given in terms of three quantum numbers. * Calculate the Fermi energy for N particles of mass m in a 3D cubic “box” of side L.4
Identical Particles
It is not possible to tell the diﬀerence between two electrons. Ignore spin for this problem.
11. They must be made in pairs. E= h π2 ¯ 2 2 (n + n2 + n2 ) y z 2mL2 x
The number of states with inside some (n2 + n2 + n2 )max ( 1 of a a sphere in n space) is x y z 8 N=
3 14 2 π(n2 + n2 + n2 )max x y z 83
. ψ = ui (x1 )uj (x2 ) → ui (x1 )uj (x2 ) − uj (x1 )ui (x2 ) (Usually we write a state like ui (x1 )uj (x2 ) when what we mean is the antisymmetrized version of that state ui (x1 )uj (x2 ) − uj (x1 )ui (x2 ). The fact that no two fermions can be in the same state means they take up space. like the photon. always have the +1 quantum number. By our symmetry. Bosons can be made singly and are their own antiparticle as can be seen from any light. P12 ψ± = ±ψ It turns out that both possibilities exist in nature.196
11. called bosons. If any two fermions are in the same state. always have the 1 quantum number. x2 ) = ψ(x1 . this operator commutes with H so we can have simultaneous eigenfunctions of energy and interchange. the interchange symmetry diﬀerence makes fermions behave like matter and bosons behave like energy. In fact. We deﬁne the interchange operator P12 . P12 ψ(x1 . there is a clear symmetry in nature under the interchange of any two electrons. x1 ) P12 P12 ψ(x1 . The are spin onehalf particles and are called fermions. There is an important distinction between fermions and bosons which we can derive from the interchange symmetry. we get back to the original state. unlike bosons. the wave function must be zero in order to be odd under interchange. Some particles like the electron. They are integer spin particles.
what is the Fermi energy of this system? You may assume that there are 2 spin states for these fermions. If the Fermi energy is deﬁned as the energy of the highest energy particle. π 6N π
2 3
(n2 + n2 + n2 )max = x y z The energy corresponding to this is the Fermi energy. h π2 ¯ 2 EF = 2mL2 6N π
2 3
2.197 So for N particles ﬁlling the levels.
2 (n2 + n2 + n2 )max = x y z 3
6N .
. The particles go into the lowest energy states possible. * We put N fermions of mass m into a (cold) one dimensional box of length L.
These will be of the form. they must both be equal to a constant which we call x . (since there are 3 degrees of freedom). In order for the two sides to be equal everywhere. The x part of the solution satisﬁes the equation Hx u(x) = Treating the other components similarly we get Hy v(y) = y v(y) Hz w(z) = z w(z)
x u(x). V (r) = V1 (x) + V2 (y) + V3 (z) In this case.
.nz = unx. Enx.
12. we can solve the problem by separation of variables.
and the total energy is E=
x
+
y
+
z.ny. H = Hx + H y + H z The energies are h π2 ¯ 2 2 (n + n2 + n2 ).ny. there will often be degenerate states.nz (r) = sin ny πy nz πz nx πx sin sin L L L
For a cubic box like this one.
There are only a few problems which can be worked this way but they are important. It can be written as a sum of terms. H = Hx + Hy + Hz (Hx + Hy + Hz )u(x)v(y)w(z) = Eu(x)v(y)w(z) [Hx u(x)] v(y)w(z) + u(x) (Hy + Hz ) v(y)w(z) Hu(x) (Hy + Hz )v(y)w(z) =E− u(x) v(y)w(z) = = Eu(x)v(y)w(z)
x
The left hand side of this equation depends only on x. The potential is zero inside the cube of side Land inﬁnite outside.198
12
3D Problems Separable in Cartesian Coordinates
We will now look at the case of potentials that separate in Cartesian coordinates.1
Particle in a 3D Box
An example of a problem which has a Hamiltonian of the separable form is the particle in a 3D box. while the right side depends on y and z. y z 2mL2 x They depend on three quantum numbers.
and all the states with energies larger than EF are empty. that energy is called the Fermi energy.) π2 ¯ 2 2 h h π2 ¯ 2 2 (nx + n2 + n2 ) = r < EF y z 2 2mL 2mL2 n Since the energy goes like n2 + n2 + n2 . the idea of the Fermi energy is still valid. In fact.1 Filling the Box with Fermions
If we ﬁll a cold box with N fermions. if the temperature is low enough. All the states with energies lower than EF are ﬁlled. The factor of 1 8 indicates that we are just using one eighth of the sphere in nspace because all the quantum numbers must be positive. (Non zero temperature will put some particles in excited states. they will go into the lowest energy N states.
. This is an approximate counting of the number of states based on the volume of a sphere in nspace. it makes sense to deﬁne a radius rn in nspace out to which x y z the states are ﬁlled. but.199 12. they will all go into diﬀerent lowenergy states.
ny Unoccupied States
rn
Fermi Surface
Occupied States nx
nz
The number of states within the radius is N = (2)spin 14 3 πr 83 n
where we have added a factor of 2 because fermions have two spin states.1. If we ﬁll up all the states up to some energy.
h h π2 ¯ 2 2 π2 ¯ 2 EF = rn = 2mL2 2mL2 3N π
2 3
h π2 ¯ 2 = 2m
3N πL3
2 3
h π2 ¯ 2 = 2m
3n π
2 3
We can also integrate to get the total energy of all the fermions.
rn
Etot
1 =2 8
0
π3 ¯ 2 π ¯ h h 5 h π 3 ¯ 2 rn = 4πr dr = 2 2 5 2mL 2mL 10mL2
2r
2 2 2
3N π
5 3
h π3 ¯ 2 = 10m
3n π
5 3
L3
where the last step shows how the total energy depends on the number of particles per unit volume n. not the volume and the N independently. dE P Etot P P = = = = = F · ds = P Ads = P dV ∂Etot − ∂V h π3 ¯ 2 10m h π3 ¯ 2 15m h π3 ¯ 2 15m 3N π 3N π 3N π
5 3
V −3 V −3 L
−5
5
2
5 3
5 3
h π3 ¯ 2 = 15m
3n π
5 3
The last step veriﬁes that the pressure only depends on the density. π3 ¯ 2 h P = 15m 3N π
5 3
L
−5
h π3 ¯ 2 = 15m
3N π
5 3
V
−5 3
.1.
h π 2 ¯ 2 3N EF = 2m πL3 π3 ¯ 2 3N h Etot = 10mL2 π
2 3
5 3
12. White Dwarfs are held up by electrons and Neutron Stars are held up by neutrons in a much smaller box.200 We can now relate the Fermi energy to the number of particles in the box.2
Degeneracy Pressure in Stars
The pressure exerted by fermions squeezed into a small box is what keeps cold stars from collapsing. The step in which EF and Etot is related to N is often useful. as it should. We can compute the pressure from the dependence of the energy on the volume for a ﬁxed number of fermions. We will use. It makes sense that this energy is proportional to the volume.
R= 3 4π h π3 ¯ 2 15me
2 3
3Ne π
5 3
V −3
5
π3 ¯ 2 h 2 3Gme MN
3 π
5 3
Ne3 N2
5
There are about two nucleons per electron N ≈ 2Ne so the radius becomes. the size of the earth. A white dwarf is the remnant of a normal star. we must compare this to the pressure of gravity. It has used up its nuclear fuel. the pressure from electrons is. Since the pressure from
. we get. For a white dwarf. until most of what is left is Fe56 which is the most tightly bound nucleus. N = 1057 . fusing light elements into heavier ones. more signiﬁcantly. ignoring general relativity and.
R
E
=
−
0 R
GMinside 4πr2 ρ dr r G( 4 πr3 ρ)4πr2 ρ 3 dr r
=
−
0
=
3GM 2 (4π)2 2 5 Gρ R = − − 15 5R
The mass of the star is dominated by nucleons. We compute this approximately. M = N MN Putting this into our energy formula. the variation of gravitational pressure with radius. Pe = We can solve for the radius. 3 E = − G(N MN )2 5 We can now compute the pressure. For one solar mass.2 MeV. 1 ∂E = − G(N MN )2 Pg = − ∂V 5 4π 3
1 3
4π 3
1 3
V −3
1
V −3
4
The pressures must balance. It is stopped by the pressure of electrons. Now the star begins to cool and to shrink. we get a radius of 7200 km. R= 81π 2 512
1 3
h ¯2 −1 3 2 N Gme MN
The radius decreases as we add mass.201 To understand the collapse of stars. The Fermi energy is about 0.
E=
nx + ny + nz +
3 2
h ¯ω
ψnx. This collapse is probably brought about by general relativistic eﬀects. this problem can also be solved nicely in spherical coordinates using rotational 2 symmetry. When they have just enough. converting protons into neutrons. y. aided by strange quarks. We can estimate the neutron star radius. z) = unx (x)uny (y)unz (z)
This was really easy. The boundary between ﬁlled and unﬁlled energy levels is a plane deﬁned by nx + ny + nz = 3 EF − h ¯ω 2
. Lets assume the central potential so we can compare to our later solution. V = 1 mω 2 r2 . The Hamiltonian is H H H p2 1 + mω 2 r2 2m 2 p2 1 1 1 p2 p2 y x + mω 2 x2 + + mω 2 y 2 + z + mω 2 z 2 = 2m 2 2m 2 2m 2 = Hx + H y + H z =
The problem separates nicely. This problem has a diﬀerent Fermi surface in nspace than did the particle in a box.202 the electrons grows faster than the pressure of gravity. the Fermi energy goes up and it becomes possible to absorb the electrons into the nucleons. For the case of a central potential.nz (x. The brightness of this type of supernova has been used to measure the accelerating expansion of the universe. the star collapses suddenly down to a size for which the Fermi pressure of the neutrons stops the collapse (with quite a shock). The Fermi energy needs to be above 1 MeV. R→R
12. The cartesian solution is easier and better for counting states though.ny. The supernovae are all nearly identical since the dwarfs are gaining mass very slowly. the star will stay at about earth size even when it cools. it collapses to become a black hole. We could have three diﬀerent spring constants and the solution would be as simple. If the pressure at the center of a neutron star becomes too great.2
The 3D Harmonic Oscillator
The 3D harmonic oscillator can also be separated in Cartesian coordinates. MN 1 − 5 N 3 2 3 = 10 me Its about 10 kilometers. If the star is more massive. Actually some white dwarfs stay at earth size for a long time as they suck in mass from their surroundings. If the electrons disappear this way. they collapse forming a neutron star and making a supernova. giving us three independent harmonic oscillators.
* N identical fermions are bound (at low temperature) in a potential V (r) = 1 mω 2 r2 . and “tallness” T . W = 1a.5a. a particle of mass m is bound in a potential V (r) =
√ −e . Find the energy eigenvalues in terms of a set of three quantum numbers (which correspond to 3 mutually commuting operators). Find the 2 energy eigenstates in terms of 3 quantum numbers. A particle of mass m is bound in the 3 dimensional potential V (r) = kr2 . (N is large. be eigenfunctions of H. y. 5. That is. you may h assume that it is α(EF /¯ ω)3 . A particle is in a cubic box. c) Find the Fermi Energy EF for N particles in the box. Solve this problem in o the simplest way possible to ﬁnd the eigenenergies in terms of a set of ”quantum numbers” that describe the system. a) Find the energy levels for this particle. z) = 1 k(x2 + 2y 2 + 3z 2 ). and T = 0. What is the energy of the ground state and ﬁrst excited state? 2. o
. If you are having trouble ﬁnding the number of states with energy less than EF . b) Find the number of states (level of degeneracy) at each of these three energies. 6. Find operators that commute 2 with the Hamiltonian and use them to simplify the Schr¨dinger equation. 4. That is. In 3 dimensions. Find the number of states (level of degeneracy) at each of these 3 energies. Find the Fermi energy of the system. b) Determine the number of degenerate states for the ﬁrst three energy levels. Use 2 separation in Cartesian coordinates to ﬁnd the energy eigenvalues in terms of a set of three quantum numbers (which correspond to 3 mutually commuting operators).) 7. What other operators can they be eigenfunctions of? b) Simplify the three dimensional Schr¨dinger equation by using these operators. width W . 8. A particle of mass m is in the potential V (r) = 1 mω 2 (x2 + y 2 ). a) Find the three lowest allowed energies. What are the energies of the three lowest energy states if L = 2a. a) Find the energy levels for this particle. 11. the potential is zero inside a cube of side L and inﬁnite outside. 3. b) Determine the number of degenerate states for the ﬁrst three energy levels. of course. 9.203
12. Find the 3 lowest allowed energies. A particle of mass m is in a cubic box. 10. A particle of mass m is bound in the 3 dimensional potential V (r) = kr2 . the potential is zero inside a cube of side L and inﬁnite outside the cube.3
Sample Test Problems
1. A particle of mass m in 3 dimensions is in a potential V (x. A particle is conﬁned in a rectangular box of length L. x2 +z 2
2
a) The deﬁnite energy states will.
however. Recall that we are looking for a set of mutually commuting operators to label our energy eigenstates. Li ] = 0
These commutators lead us to choose the mutually commuting set of operators to be H.1
Angular Momentum
Rotational Symmetry
If the potential only depends on the distance between two particles. o −¯ 2 2 h ∇ uE (r) + V (r)uE (r) 2μ −¯ 2 h 2μ 1 r2 r ∂ ∂r
2
= EuE (r) = EuE (r)
+
L2 1 ∂ − 2 uE (r) + V (r)uE (r) r ∂r ¯ r2 h
.1). we can show that the Angular Momentum operators commute with the Hamiltonian (See section 13. The components of angular momentum do not commute (See section 13.2) with each other [Lx . If a the Hamiltonian has rotational symmetry.204
13
13. We actually want two operators plus H to give us three quantum numbers for states in three dimensions. L2 . Ly ] = i¯ Lz h
12.3) with only radial derivatives and L2 . We know from classical mechanics that these are important problems. This is true for the coulomb (and gravitational) potential as well as many others.
[Li .4. We could have chosen any component. and Lz .4. Lj ] = i¯ h
ijk Lk
but the square of the angular momentum commutes with any of the components
[L2 . The Schr¨dinger equation can now be rewritten (See section 13. Li ] = 0 We therefore expect each component of L to be conserved. [H. it is most convenient to choose Lz given the standard deﬁnition of spherical coordinates. We will not be able to label our states with the quantum numbers for the three components of angular momentum. V (r) = V (r) the Hamiltonian has Rotational Symmetry.4.
Since o Lz does not appear in the Schr¨dinger equation.
. φ) h 2 ( + 1) 1 ∂ ∂ − + RE (r) + V (r)RE (r) = ERE (r) r ∂r r ∂r r2
By assuming the eigenvalues of L2 have the form ( + 1)¯ 2 . This radial equation can be simpliﬁed a bit. since the units of angular momentum are those of ¯ and since we expect L2 to h have positive eigenvalues. we have anticipated the solution but h not constrained it.
−¯ 2 h 2μ
1 r2
L2 Y m (θ. We get the three equations. Write the o solution as a product
uE (r) = RE (r)Y
m (θ. For = 0. we only label the radial solutions with the energy and the eigenvalues of . For any given problem with rotational symmetry. Y
m L 2
Y
m
= Lx Y
m Lx Y m
+ Ly Y
m Ly Y m
+ Lz Y
m Lz Y m
≥0
h The assumption that the eigenvalues of Lz are some (dimensionless) number times ¯ does not constrain our solutions at all. φ)
where labels the eigenvalue of the L2 operator and m labels the eigenvalue of the Lz operator.
−¯ 2 ∂ 2 h 2 ∂ ( + 1)¯ 2 h + RE (r) + V (r) + 2μ ∂r2 r ∂r 2μr2
RE (r) = ERE (r)
We have grouped the term due to angular momentum with the potential. φ) = m¯ Y m (θ.205 This leads to a great simpliﬁcation of the 3D problem. It is often called a pseudopotential. We will use the algebra of the angular momentum operators to help us solve the angular part of the problem in general. φ) h Lz Y m (θ. φ) = ( + 1)¯ 2 Y m (θ. we will need to solve a particular diﬀerential equation in one variable r. it is like a repulsive potential. It is possible to separate the Schr¨dinger equation since r and L2 appear separately.
. we deﬁne the operator L+ and its Hermitian conjugate L− .
L+
. L± ] = 0 and [L± . To progress toward the possible quantization of angular momentum variables in 3D.. it commutes with these operators. Li ] = i¯ Lz h i¯ ijk Lk h 0.. Ly ] = [Li . Lz ] ± i[Ly . L+ raises the z component of angular momentum by one unit of ¯ and L− lowers it by one h unit.206
13.5) L± on the eigenstates Y m . Lz ] = [Lx . = h ( + 1) − m(m ± 1)Y ¯
(m±1)
Therefore. L+ Y = 0. the lowering stops because L− Y − = 0. .
We have shown that angular momentum is quantized for a rotor with a single angular variable. Lz ] = ∓¯ L± .2
Angular Momentum Algebra: Raising and Lowering Operators
We have already derived the commutators of the angular momentum operators [Lx . L± ] = 0 The commutator with Lz is. Lj ] = [L2 . 2. show that is an integer greater than or equal to 0.. Similarly.. . L± ≡ Lx ± iLy . and in so doing. [L2 . and that m is also an integer
L± Y
m
= 0. [L± . h h From the commutators [L2 .4. The raising stops when m = and the operation gives zero. − ≤m≤ m = − . 1. − + 1. Since L2 commutes with Lx and Ly .
l=0 l=1 l=2
L+ L+ L+ L+ L+ L L L+ L+ L+ L+ L L L L L L L L 
m 4 3 2 1 0 1 2 3 4
Solution to radial equation depends on l. Lz ] = i¯ (−Ly ± iLx ) = ∓¯ L± . we can derive the eﬀect of the operators h (See section 13.
Ly ] = h(Lz + Lz ) = 2¯ Lz ¯ h L2 = L+ L− + L2 − ¯ Lz . leaving unchanged.3
The Angular Momentum Eigenfunctions
The angular momentum eigenstates are eigenstates of two operators.
Lz Y m (θ. Lx ] − i[Lx .
Note that we can easily write the components of angular momentum in terms of the raising and lowering operators. φ) = m¯ Y m (θ. φ)
−
13.2: What is the expectation value of Lx in the state ψ(r) = R(r)(
1 3 Y10 (θ. φ) h L2 Y m (θ. φ))?*
2 3 Y11 (θ. φ))?*
2 3 Y11 (θ. Lx Ly = = 1 (L+ + L− ) 2 1 (L+ − L− ) 2i
We will also ﬁnd the following equations useful (and easy to compute). The raising and lowering operators L± = Lx ± iLy raise or lower m.1: What is the expectation value of Lz in the state ψ(r) = R(r)( i
1 3 Y1−1 (θ. L− ] = i[Ly .5.207 Angular momentum is quantized. Any measurement of the total angular momentum gives the somewhat curious h result ( + 1)¯ h L = where is an integer. φ)
−
* See Example 13. Any measurement of a component of angular momentum will give some integer times ¯ . φ) = ( + 1)¯ 2 Y m (θ.5. We have no additional knowledge about Lx and Ly since these operators don’t commute with Lz . h z
* See Example 13. [L+ . φ) h
All we know about the states are the two quantum numbers and m.
L± Y
m
=h ¯
( + 1) − m(m ± 1)Y
(m±1)
.
φ) m (θ. The state with maximum m must give zero when raised. Therefore. dΘ(θ) + iΘ(θ) cot θ(i ) = 0 dθ dΘ(θ) = cot θΘ(θ) dθ The solution is Θ(θ) = C sin θ. dΘ = C cos θ sin dθ
−1
θ = cot θΘ
Its correct. If we were to use halfintegers. Here we should note that only the integer value of work for these solutions.208 The diﬀerential operators take some work to derive (See section 13. the eigenstate Y is. for example at φ = 0 and φ = 2π. Y Lz Y
m (θ.4). φ)
=
h ¯ ∂ h ¯ Θ(θ)eimφ = imΘ(θ)eimφ = m¯ Y h i ∂φ i
To ﬁnd the θ dependence.4.
Y = C sin (θ)ei
φ
We can compute the next state down by operating with L− . for which no θ or φ coordinates exist. we will use the fact that there are limits on m. Y
( −1)
= CL− Y
. Check the solution. We will ﬁnd later that the halfinteger angular momentum states are o used for internal angular momentum (spin). L+ Y = heiφ ¯ ∂ ∂ + i cot θ ∂θ ∂φ Θ (θ)ei
φ
=0
This gives us a diﬀerential equation for that state.
Lz = L± = he±iφ ¯
h ¯ ∂ i ∂φ ∂ ∂ + i cot θ ± ∂θ ∂φ
Its easy to ﬁnd functions that give the eigenvalue of Lz . Even though the probability may be single valued. φ)
= Θ(θ)Φ(φ) = Θ(θ)eimφ
m (θ. the wave functions would not be single valued. discontinuities in the amplitude would lead to inﬁnities in the Schr¨dinger equation.
1 2π
d(cos θ)
−1 0
dφ Y ∗ Y m dΩ Y ∗ Y m
m
=1
m
=1
Since they are eigenfunctions of Hermitian operators.
dΩ Y ∗ Y m
m
= δ δmm
We will use the actual function in some problems.
∞ ∞
Y
=0 m=−
m
Y
m
=
=0 m=−
 m
m = 1
. they are orthogonal.
Y
(−m)
= (−1)m Y ∗ m
Any function of θ and φ can be expanded in the spherical harmonics. The spherical harmonics are normalized.
∞
f (θ.209 We can continue to lower m to get all of the eigenfunctions. φ) =
=0 m=−
C
m Y m (θ. Y00 Y11 Y10 Y22 Y21 Y20 = 1 √ 4π
3 iφ e sin θ 8π 3 cos θ = 4π 15 2iφ e = sin2 θ 32π 15 iφ e sin θ cos θ = − 8π 5 (3 cos2 θ − 1) = 16π = −
The spherical harmonics with negative m can be easily compute from those with positive m. φ)
The spherical harmonics form a complete set. We call these eigenstates the Spherical Harmonics.
210 When using braket notation.4.4
13. therefore. L− does not change under parity and all the Y m with have the same parity as Y L− Y → (−1) L− Y Y
m (π
− θ. Y (θ. the parity operation is r → r
θ → π−θ φ → φ + π. We know the state Y parity transformation gives.
The radial part of the wavefunction. φ) → Y (π − θ. Y 0 (θ.1
Derivations and Computations
Rotational Symmetry Implies Angular Momentum Conservation
In three dimensions.3. The spherical harmonics are related to the Legendre polynomials which are functions of θ. φ + π) = ei φ ei
π
in general. A
sin (θ) = ei π Y = (−1) Y
The states are either even or odd parity depending on the quantum number . parity = (−1)
The angular momentum operators are axial vectors and do not change sign under a parity transformation.1
Parity of the Spherical Harmonics
In spherical coordinates. this means that we can change our coordinates by rotating about any one of the axes and the equations should not change. φ) Y = = 2 +1 4π (−1)
m
1 2
P (cos θ) 2 + 1 ( − m)! 4π ( + m)!
1 2
m
P m (cos θ)eimφ
13. Therefore. Lets try and inﬁnitesimal rotation about the z axis.  m is suﬃcient to identify the state. φ + π) = (−1) Y
m (θ. is unchanged and the R(r) → R(r) parity of the state is determined from the angular part. φ)
13. The x
.
Lx ] = [H. Note that we have inserted the constant of angular momentum. H. Lz ] = [H. however. z) + Hdθ Subtract oﬀ the original equation. x = x + dθy y = y − dθx
The original Schr¨dinger Equation is o Hψ(x.4. the square of the angular momentum vector commutes with all the components. [H. Now we Taylor expand this equation. H ∂ ∂ y− x ψ= ∂x ∂y ∂ ∂ y− x Hψ ∂x ∂y ∂ψ ∂ψ y− x ∂x ∂y = Eψ(x. z) and the transformed equation is Hψ(x + dθy. Ly ] = 0.
h ¯ i
h ¯ i
x
∂ ∂ −y ∂y ∂x
=0
in anticipation of identifying this operator as the z component L=r×p
Lz =
h ¯ i
x
∂ ∂ −y ∂y ∂x
= xpy − ypx
We could have done inﬁnitesimal rotations about the x or y axes and shown that all the components of the angular momentum operator commute with the Hamiltonian.2
The Commutators of the Angular Momentum Operators
[Lx . y. [L2 . y.211 and y coordinates will change. y − dθx. z) + Edθ ∂ψ ∂ψ y− x ∂x ∂y
We ﬁnd an operator that commutes with the Hamiltonian.
13. y − dθx. z) = Eψ(x. z) = Eψ(x + dθy. Lz ] = 0
. y. Ly ] = 0 Remember that operators that commute with the Hamiltonian imply physical quantities that are conserved. Hψ(x. z). y.
It is commonly used for a cross product. y and z. L2 = L2 + L2 + L2 x y z [Lz . problems will be greatly simpliﬁed.3
Rewriting
p2 2μ
Using L2
We wish to use the L2 and Lz operators to help us solve the central potential problem. Now lets compute commutators of the L2 operator. where we know the commutators. and remove all the angular derivatives. we can generalize this to [Li .
ijk
=−
jik
=−
ikj
=−
kji
The tensor is equal to 1 for cyclic permutations of 123. L2 ] + [Lz . zpx − xpz ] = y[pz . L2 ] = 0. Lx ]Lx + Lx [Lz . L2 commutes with every component of L. equal to 1 for anticyclic permutations. Ly ]Ly + Ly [Lz . L2 ] x y [Lz . pz ]py x h ¯ [ypx − xpy ] = i¯ Lz = h i
Since there is no diﬀerence between x. For example. Lx ] + [Lz .4. First. z]px + [z. [Lx . Lj ] = i¯ h where
ijk ijk Lk
is the completely antisymmetric tensor and we assume a sum over repeated indices. write out L2 . L2 ] = = =
We can generalize this to [Li . Lets just compute the commutator. If we can rewrite H in terms of these operators. Ly ] i¯ (Ly Lx + Lx Ly − Lx Ly − Ly Lx ) = 0 h
ijk
[Lz . We will work in Cartesian coordinates for a while. and equal to zero if any index is repeated.212 This will give us the operators we need to label states in 3D central potentials. Ly ] = [ypz − zpy .
13. L2 = = (r × p)2 −¯ 2 h y ∂ ∂ −z ∂z ∂y
2
+ z
∂ ∂ −x ∂x ∂z
2
+ x
∂ ∂ −y ∂y ∂x
2
. if L=r×p then Li = rj pk where we again assume a sum over repeated indices.
o p2 = = 1 L2 + (r · p)2 − i¯ r · p h r2 2 1 ∂ h 1 2 ¯2 ∂ L − 2 r − ¯2 h r2 r ∂r r ∂r
The Schr¨dinger equation now can be written with only radial derivatives and L2 .4
Spherical Coordinates and the Angular Momentum Operators
The transformation from spherical coordinates to Cartesian coordinate is.4.213 Group the terms. x y z = = = r sin θ cos φ r sin θ sin φ r cos θ
. things simplify a lot. o −¯ 2 h 2μ 1 r2 r ∂ ∂r
2
+
L2 1 ∂ − 2 2 uE (r) + V (r)uE (r) = EuE (r) r ∂r ¯ r h
13. L2 + (r · p)2 = r2 p2 + i¯ r · p h We can now solve for p2 and we have something we can use in the Schr¨dinger equation. L2 = − h ¯ 2 x2 ∂2 ∂2 ∂2 ∂2 ∂2 ∂2 + 2 + y2 + 2 + z2 + 2 2 2 2 ∂z ∂y ∂x ∂z ∂x ∂y 2 2 2 ∂ ∂ ∂ ∂ ∂ ∂ + 2yz + 2xz + 2x + 2y + 2z − 2xy ∂x∂y ∂y∂z ∂x∂z ∂x ∂y ∂z
We expect to need to keep the radial derivatives so lets identify those by dotting r into p. This will also make the units match L2 . (r · p)2 = = ∂ ∂ ∂ +y +z ∂x ∂y ∂z ∂2 ∂2 ∂2 ∂2 ∂2 ∂2 −¯ 2 x2 2 + y 2 2 + z 2 2 + 2xy h + 2yz + 2xz ∂x ∂y ∂z ∂x∂y ∂y∂z ∂x∂z ∂ ∂ ∂ +y +z +x ∂x ∂y ∂z −¯ 2 x h
2
By adding these two expressions.
We use the chain rule and the above transformation from 1 Cartesian to spherical. We have used d cos θ = − sin θdθ and d tan φ = cos2 φ dφ.
∂ ∂x
= = = =
∂ ∂y
= = = =
∂ ∂z
=
∂r ∂ ∂ cos θ ∂ ∂ tan φ ∂ + + ∂x ∂r ∂x ∂ cos θ ∂x ∂ tan φ x ∂ −xz −1 ∂ y ∂ + 3 − 2 cos2 φ r ∂r r sin θ ∂θ x ∂φ 1 1 ∂ 1 sin θ sin φ ∂ ∂ + sin θ cos φ cos θ − sin θ cos φ cos2 φ ∂r r sin θ ∂θ r sin2 θ cos2 φ ∂φ 1 ∂ 1 sin φ ∂ ∂ + cos φ cos θ − sin θ cos φ ∂r r ∂θ r sin θ ∂φ ∂r ∂ ∂ cos θ ∂ ∂ tan φ ∂ + + ∂y ∂r ∂y ∂ cos θ ∂y ∂ tan φ y ∂ −yz −1 ∂ 1 ∂ + 3 + cos2 φ r ∂r r sin θ ∂θ x ∂φ ∂ 1 1 ∂ 1 1 ∂ sin θ sin φ + sin θ sin φ cos θ + cos2 φ ∂r r sin θ ∂θ r sin θ cos φ ∂φ ∂ 1 ∂ 1 cos φ ∂ sin θ sin φ + sin φ cos θ + ∂r r ∂θ r sin θ ∂φ ∂r ∂ ∂ cos θ ∂ ∂ tan φ ∂ + + ∂z ∂r ∂z ∂ cos θ ∂z ∂ tan φ
.214 The transformation from Cartesian coordinates to spherical coordinates is. Ultimately all of these should be written in the sperical cooridnates but its convenient to use x for example in intermediate steps of the calculation. r cos θ tan φ = = = y x x2 + y 2 + z 2 z x2 + y 2 + z 2
z
θ
r y
φ x
We now proceed to calculate the angular momentum operators in spherical coordinates. The ﬁrst step ∂ is to write the ∂xi in spherical coordinates.
we have. ∂ ∂x ∂ ∂y ∂ ∂z = = = ∂ 1 ∂ 1 sin φ ∂ + cos φ cos θ − ∂r r ∂θ r sin θ ∂φ ∂ 1 ∂ 1 cos φ ∂ sin θ sin φ + sin φ cos θ + ∂r r ∂θ r sin θ ∂φ ∂ 1 ∂ cos θ − sin θ ∂r r ∂θ sin θ cos φ
Now simply plug these into the angular momentum formulae.215 z ∂ + r ∂r ∂ cos θ ∂r ∂ cos θ ∂r 1 z 2 −1 ∂ − 3 r r sin θ ∂θ 1 −1 ∂ + 1 − cos2 θ r sin θ ∂θ 1 ∂ − sin θ r ∂θ
= = =
Bringing together the above results.
Lz L±
= =
h ¯ ∂ i ∂φ he±iφ ± ¯ ∂ ∂ + i cot θ ∂θ ∂φ
. Lz L± ∂ ∂ h ¯ ∂ −y = ∂y ∂x i ∂φ ∂ ∂ ∂ h ¯ ∂ −z ±i z −x = Lx ± iLy = y i ∂z ∂y ∂x ∂z ∂ ∂ ∂ ±z ±i = h ∓(x ± iy) ¯ ∂z ∂x ∂y ∂ ∂ ∂ ± cos θ ±i = hr ∓ sin θe±iφ ¯ ∂z ∂x ∂y = h ¯ i x = h ∓ sin θe±iφ r cos θ ¯ = he±iφ ¯ = he±iφ ¯
=
h ¯ i
(y ∓ ix)
∂ −z ∂z
∂ ∂ ∓i ∂y ∂x
∂ ie±iφ ∂ ∂ ∂ ∂ − sin θ + cos θe±iφ ± ± cos θ r sin θe±iφ ∂r ∂θ ∂r ∂θ sin θ ∂φ i cos θ ∂ ∂ ∂ ± cos2 θ ± ± sin2 θ ∂θ ∂θ sin θ ∂φ ∂ ∂ + i cot θ ± ∂θ ∂φ
We will use these results to ﬁnd the actual eigenfunctions of angular momentum.
the new state is still an eigenstate of L2 with the same eigenvalue. Ly ] = L2 − L2 ∓ ¯ Lz h x y z
we can derive limits on the quantum numbers. L∓ L± = (Lx ∓ iLy )(Lx ± iLy ) = L2 + L2 ± iLx Ly ∓ iLy Lx x y = L2 + L2 ± i[Lx . L− and LZ do not change . h Since L† = L∓ . This is also true for operations with Lz . The eigenvalue of Lz is changed when we operate with L+ or L− .
(m±1)
= C± ( . m)Y
These operators raise or lower the z component of angular momentum by one unit of ¯ .) From the above equation we can see that (L± Y L± Y
m m)
is an eigenstate of Lz .5 The Operators L±
m. ± L± Y m L± Y Y m L∓ L± Y
m m
≥0 ≥0
Writing L+ L− in terms of our chosen operators. We can assume that h ≥0
. That is. L2 (Lz Y m ) = Lz L2 Y m = ( + 1)¯ 2 (Lz Y m ) h The operators L+ . we see that we have the same ( + 1) after operation.4. L± ]Y ± ¯ L± Y h
m
= m¯ (L± Y h
m)
m
= (m ± 1)¯ (L± Y h
m)
(This should remind you of the raising and lowering operators in the HO solution. Y
m (L 2
− L2 ∓ ¯ Lz )Y h z
2
m 2
≥0
( ( + 1) − m ∓ m)¯ ≥ 0 h ( + 1) ≥ m(m ± 1)
We know that the eigenvalue ( + 1)¯ 2 is greater than zero. Lz (L± Y
m)
= L± Lz Y
m
+ [Lz .216 13. ( + 1). its easy to show that the following is greater than zero.
The next step is to ﬁgure out how the L± operators change the eigenstate Y are generated when we operate with L+ or L− ? L2 (L± Y
m)
What eigenstates of L2
= L± L2 Y
m
= ( + 1)¯ 2 (L± Y h
m)
Because L2 commutes with L± . after we operate.
. m)
2
(m±1) Y (m±1)
m L± Y
m
= = =
Y Y
= ( ( + 1) − m ∓ m)¯ h C( . m)
2
m L∓ L± Y m 2 2 m (L − Lz ∓ 2
h ¯ Lz )Y
2
m
( + 1) − m2 ∓ m ¯ 2 h ( + 1) − m(m ± 1)
C± (l. L+ raises m by one and L− lowers m by one.217 because negative values just repeat the same eigenvalues of ( + 1)¯ 2 . there will be states in integer steps up to . L± Y L± Y
m L± Y m
= C( . − + 1. m) = h ¯
We now have the eﬀect of the raising and lowering operators in terms of the normalized eigenstates.. L− Y
(− )
=0
L+ Y = 0 The raising and lowering operators change m in integer steps. and does not change .5
13..5. We now know what eigenstates are allowed. m)Y
The coeﬃcient C± ( . m) can be computed. so.. starting from m = − . the raising and lowering must stop for m = ± . Since m is limited to be in the range − ≤ m ≤ . Having the minimum at − and the maximum at + with integer steps only works if is an integer or a halfinteger. φ))?
. φ)
What is the expectation value of Lz in the state ψ(r) = R(r)(
−i
1 3 Y1−1 (θ. − ≤m≤ Now. There are 2 + 1 states with the same and diﬀerent values of m. The eigenstates of L2 and Lz should be normalized Y The raising and lowering operators acting on Y L± Y
m m Y m m
= 1. − 1. m)2 Y = C( . m = − . L± Y
m
=h ¯
( + 1) − m(m ± 1)Y
(m±1)
13.1
Examples
The Expectation Value of Lz
2 3 Y11 (θ.
give
(m±1)
= C± ( . h The condition that ( + 1) ≥ m(m ± 1) then becomes a limit on m.
5. Lx ] + i[Lz .2
The Expectation Value of Lx
2 3 Y11 (θ. [L2 .6
Sample Test Problems
m
1. L+ ] = 0. L+ ] = [Lz . L+ ]. L+
[Lz . Now show that L+ Y raises the Lz eigenvalue but does not change the L2 eigenvalue. Ly ] = i¯ (Ly − iLx ) = h(Lx + iLy ) = hL+ h ¯ ¯ We have the commutators. m m)
= L2 L+ Y
m)
m
− L+ L2 Y
=0
L2 (L+ Y
= ( + 1)¯ 2 (L+ Y h
. ψLx ψ = = 1 2 1 2 h ¯ 2 2 Y11 − 3 2 Y11 − 3 2 Y11 − 3
−
1 3 Y10 (θ. Derive the commutators [L2 . The angular part is properly normalized. φ))?
1 Y10 L+ + L−  3 1 Y10  3 1 Y10  3
2 Y11 − 3
1 Y10 3
2 L− Y11 − 3 2√ 2Y10 − 3
1 L+ Y10 3 1√ 2Y11 3
= =
h ¯2 2 (−1 − 1) = − ¯ h 23 3
13. L+ ] and [Lz . ψLz ψ = 2 Y11 − i 3 2 Y11 − i 3 2 1 − 3 3 h ¯= 1 Y1−1 Lz  3 1 Y1−1  3 1 h ¯ 3 2 Y11 − i 3 1 Y1−1 3 1 h ¯ Y1−1 3
= =
2 h ¯ Y11 + i 3
13. L+ ]Y
m m. Lx + iLy ] = [Lz .
= CY
(m+1) . φ)
What is the expectation value of Lx in the state ψ(r) = R(r)( We need Lx = (L+ + L− )/2. Now we apply them to a Y [L2 . Answer L+ = Lx + iLy Since L2 commutes with both Lx and Ly .
that is.218 The radial part plays no role.
if the Hamiltonian is symmetric under rotations.219 So. Find the coeﬃcients a. Lx ] and [L2 . each term must be zero. In 3 dimensions. Calculate the following commutators: [x. Write the (normalized) state which is an eigenstate of L2 with eigenvalue ( + 1)¯ 2 = 2¯ 2 and h h also an eigenstate of Ly with eigenvalue 1¯ in terms of the usual Y m . [ 1 mω 2 r2 . 2 8. 7. A particle is in a l = 1 state and is known to have angular momentum in the x direction equal to +¯ . L+ raises the eigenvalue of Lz .1 + bY1.
. [L+ . 3. Answer An eigenvalue of ( + 1)¯ 2 = 2¯ 2 implies = 1. a particle is in the state: ψ(r) = C(iY33 − 2Y30 + 3Y31 ) R(r) where R(r) is some arbitrary radial wave function normalized such that
∞ 0
R∗ (r)R(r)r2 dr = 1. h 4. x 5. Prove that. Lz ]. 9. h ¯ That is Lx ψ = hψ. L+ ]Y
m
m
= Lz L+ Y
m)
m
− L+ Lz Y
m)
m
= hL+ Y ¯
m)
m
Lz (L+ Y
− m¯ (L+ Y h
m)
= h(L+ Y ¯
m)
Lz (L+ Y So. ψ must have the form ψ = R(r)(aY1. and c for ψ normalized. not normalizable to 1. B=0 A = −C The state is 1 √ (Y11 − Y1−1 ) 2
The trivial solution that A = B = C = 0 is just a zero state.
6. Derive the relation L+ Y
m
=h ¯
( + 1) − m(m + 1)Y
(m+1) . Lz ]. Lz ] = 0. [Lz . We will need a linear combination of the Y1m to h h get the eigenstate of Lx = L+ +L− . b. Since we know l = 1.0 + cY1.
= (m + 1)¯ (L+ Y h
h h 2. L2 ]. px ].−1 ). 2 L+ + L− (AY11 + BY10 + CY1−1 ) = 0 2 h ¯ √ (AY10 + BY11 + BY1−1 + CY10 ) = 0 2 (BY11 + (A + C)Y10 + BY1−1 ) = 0 Since this is true for all θ and φ. L+ does not change . Write the (normalized) state which is an eigenstate of L2 with eigenvalue ( + 1)¯ 2 = 2¯ 2 and h also an eigenstate of Lx with eigenvalue 0¯ in terms of the usual Y m . then [H. L+ Y is also an eigenfunction of L2 with the same eigenvalue. Calculate the commutators [pz .
what are the possible measured values and what are probabilities for each.1
The Radial Equation and Constant Potentials *
The Radial Equation *
After separation of variables.
14
14. Two (diﬀerent) atoms of masses M1 and M2 are bound together into the ground state of a diatomic molecule. The binding is such that radial excitations can be neglected at low energy and that the atoms can be assumed to be a constant distance a = 3˚ apart.
11.
−¯ 2 ∂ 2 h 2 ∂ ( + 1)¯ 2 h + Rn (r) + V (r) + 2μ ∂r2 r ∂r 2μr2
Rn (r) = ERn (r)
This pseudopotential repels the particle from the origin. write down the energy eigenfunctions for the ground state and the ﬁrst excited state. 10. (We will ignore the small spread A around r = a. −¯ 2 h 2μ 1 r2 r ∂ ∂r
2
+
( + 1) 1 ∂ RE (r) + V (r)RE (r) = ERE (r) − r ∂r r2
It can be simpliﬁed a bit. c) Assuming that both masses are about 1000 MeV.) a) What is the energy spectrum due to rotations of the molecule? b) Assuming that R(r) is given. −¯ 2 ∂ 2 h 2 ∂ ( + 1)¯ 2 h + Rn (r) + V (r) + 2 2 2μ ∂r r ∂r 2μr Rn (r) = ERn (r)
. the radial equation depends on . b) If a measurement of Lz is made. −¯ 2 ∂ 2 h ( + 1) 2 ∂ − + RE (r) + V (r)RE (r) = ERE (r) 2μ ∂r2 r ∂r r2 The term due to angular momentum is often included with the potential.220 a) Find the value of C that will normalize this wave function.2
Behavior at the Origin *
The pseudopotential dominates the behavior of the wavefunction at the origin if the potential is less singular than r12 .
14. c) Find the expected value of < Lx > in the above state. how does the excitation energy of the ﬁrst excited state compare to thermal energies at 300◦K.
The ﬁrst solution. s = . The second solution.221 For small r.
. ρ = kr → iκr The full regular solution of the radial equation for a constant potential for a given j (ρ) = (−ρ) 1 d ρ dρ sin ρ ρ is
the spherical Bessel function... n (ρ) → 1 · 3 · 5 · . is well behaved at the origin (regular solution). j (ρ) → ρ 1 · 3 · 5 · .3
Spherical Bessel Functions *
We will now give the full solutions in terms of ρ = kr. causes normalization problems at the origin (irregular solution). but are not dominant.
14.(2 + 1) ρ +1
The lowest
Bessel functions (regular at the origin) solutions are listed below. s = and s = − − 1. s = − − 1. Higher powers of r are OK. s(s − 1) + 2s = ( + 1) s(s + 1) = ( + 1) There are actually two solutions to this equation. the Bessel function has the following behavior. For small r. These are written for E > V but can be are also valid for E < V where k becomes imaginary.. Plugging this into the equation we get s(s − 1)rs−2 + 2srs−2 − ( + 1)rs−2 = 0.. For small r.(2 + 1) is
The full irregular solution of the radial equation for a constant potential for a given n (ρ) = −(−ρ) 1 d ρ dρ cos ρ ρ
the spherical Neumann function. the Neumann function has the following behavior. the equation becomes ∂2 2 ∂ ( + 1) + Rn (r) = 0 Rn (r) − ∂r2 r ∂r r2 The dominant term at the origin will be given by some power of r R(r) = rs .
h
(1)
(ρ) = j (ρ) + in (ρ) = (−ρ) h
(2)
1 d ρ dρ
i sin ρ − i cos ρ → − ei(ρ− ρ ρ
(1)∗
π 2 )
(ρ) = j (ρ) − in (ρ) = h
(ρ)
The functional for for large r is given. The Hankel functions of the ﬁrst type are the ones that will decay exponentially as r goes to inﬁnity if E < V . The linear combinations analogous to the complex exponentials of the 1D free particle solutions are the spherical Hankel functions.
cos ρ ρ cos ρ sin ρ n1 (ρ) = − 2 − ρ ρ 3 cos ρ 3 sin ρ cos ρ n2 (ρ) = − 3 − + ρ ρ2 ρ n0 (ρ) = −
The most general solution is a linear combination of the Bessel and Neumann functions.222
sin ρ ρ sin ρ cos ρ j1 (ρ) = 2 − ρ ρ 3 sin ρ 3 cos ρ sin ρ j2 (ρ) = − − ρ3 ρ2 ρ j0 (ρ) =
The lowest
Neumann functions (irregular at the origin) solutions are listed below. The Neumann function should not be used in a region containing the origin. (ρ >> ).
h0 (ρ) = h1 (ρ) = − h2 (ρ) =
(1) (1)
(1)
eiρ ρ
eiρ iρ 1+ i ρ
ieiρ ρ
1+
3 3i − 2 ρ ρ
We should also give the limits for large r. The lowest Hankel functions of the ﬁrst type are shown below. sin ρ − ρ cos ρ − n (ρ) → ρ j (ρ) →
π 2 π 2
.of the Bessel and Neumann functions. The Bessel and Neumann functions are analogous the sine and cosine functions of the 1D free particle solutions. so it is right for bound state solutions.
All our solutions must have equal ﬂux in and out.42
We can see both angular and radial excitations.72 6. we see that the Bessel function is composed of an incoming spherical wave and an outgoing spherical wave of the same magnitude. Outside the sphere. j (ρ) → − 1 e−i(kr− 2ikr
π/2)
− ei(kr−
π/2)
This is important.10 10.14 4.28 7. The boundary condition is that the wave function go to zero on the sphere. If the ﬂuxes were not equal. We only need to ﬁnd the zeros of the Bessel functions.42
n=3 9.73 9.99 8.
0 1 2 3 4 5
n=1 3. probability would build up at the origin. the solution is a Bessel function.
14.
V(r)
Spherical Potential Well (Bound States)
a r
V0
E
.49 5. the wavefunction is zero.5
Bound States in a Spherical Potential Well *
We now wish to ﬁnd the energy eigenstates for a spherical potential well of radius a and potential −V0 .32
n=2 6. j (ka) = 0
There are an inﬁnite number of solutions for each . The table below gives the lowest values of ka =
2ma2 E h2 ¯
which satisfy the boundary condition.223 Decomposing the sine in the Bessel function at large r. Inside the sphere.18 9.4
Particle in a Sphere *
This is like the particle in a box except now the particle is conﬁned to the inside of a sphere of radius a.
14.
A [j (ρ)]ρ=ka = B [h (ρ)]ρ=iκa Then match the ﬁrst derivative.224 We must use the Bessel function near the origin. k
dj (ρ) dρ
j (ρ)
= (iκ)
ρ=ka
dh (ρ) dρ
h (ρ)
ρ=iκa
This is often called matching the logarithmic derivative. Rn (r) = Aj (kr) k= 2μ(E + V0 ) h ¯2
We must use the Hankel function of the ﬁrst type for large r.
. we have to match the solutions at the boundary. Ak dj (ρ) dρ = B(iκ)
ρ=ka
dh (ρ) dρ
ρ=iκa
We can divide the two equations to eliminate the constants to get a condition on the energies. ρ = kr → iκr κ= Rn −2μE h ¯2 (1) = Bh (iκr)
To solve the problem. First match the wavefunction. ka iκa ka cot(ka) − 1 = −κa − 1 k cot(ka) = −κ
This is the same transcendental equation that we had for the odd solution in one dimension.
ρ=iκa
= (iκ)
ρ=ka
ieiρ iρ
−
eiρ iρ
eiρ iρ2
Dividing and substituting for ρ. For k
cos ρ sin ρ ρ − ρ2 sin ρ ρ
= 0. we get k cot(ka) − 1 1 = iκ i − . the = 0 term will be suﬃcient to describe scattering. Often. There can even be no solution. the boundary condition is . ⎞ ⎛ 2μ(E + V0 ) ⎠ −E a = − cot ⎝ 2 V0 + E h ¯ The number of solutions depends on the depth and radius of the well.
225
E V0 V0+π2h2/8ma2 0
14. To maintain the outgoing ﬂux equal to the incoming ﬂux. The scattering for each partial wave can be computed independently. For large r the Bessel function becomes j (ρ) → − so our plane wave becomes
∞
1 e−i(kr− 2ikr
π/2)
− ei(kr−
π/2)
.6
Partial Wave Analysis of Scattering *
We can take a quick look at scattering from a potential in 3D We assume that V = 0 far from the origin so the incoming and outgoing waves can be written in terms of our solutions for a constant potential. an incoming plane wave along the z direction can be expanded in Bessel functions. the most the scattering can do is change the relative phase of the incoming an outgoing waves. particularly the outgoing part.
eikz → −
=0
4π(2 + 1)i
1 e−i(kr− 2ikr
π/2)
− ei(kr−
π/2)
Y
0
The scattering potential will modify the plane wave. In fact. R (r) → − 1 e−i(kr− 2ikr
π/2)
− e2iδ
(k) i(kr− π/2)
e
=
sin(kr − π/2 + δ (k)) iδ e kr
(k)
.
∞
eikz = eikr cos θ =
=0
4π(2 + 1)i j (kr)Y
0
Each angular momentum ( ) term is called a partial wave.
for low energy scattering and short range potentials. ⎪ ⎪ ⎪ 1 ⎪ dσ ⎪ = 2⎪ ⎪ ⎪ dΩ k ⎪ ⎪ ⎪2 ⎪ ⎪ ⎪ ⎪ sin(δ )P (cos θ)⎪ ⎪ ⎪ ⎪ ⎪
∞
(2 + 1)e
=0
iδ
The phase shifts must be computed by actually solving the problem for the particular potential. R = Bj (kr) + Cn (kr) k= 2μE h ¯2
. We can compute the diﬀerential cross section for scattering dσ scattered ﬂux into dΩ ≡ dΩ incident ﬂux in terms of the phase shifts.
eikz
V
4 3 2 1 0 1 2 3 4
Only the low
partial waves get close enough to the origin to be aﬀected by the potential. the ﬁrst term = 0 is often enough to solve the problem. In fact. we can have a linear combination of functions.
14. R = Aj (k r) k = 2μ(E + V0 ) h ¯2
For large r. the energy is greater than zero.7
Scattering from a Spherical Well *
For the scattering problem.226 The δ (k) is called the phase shift for the partial wave of angular momentum . We must choose the Bessel function in the region containing the origin.
we get k B cos(ka) + C sin(ka) cos(k a) =k sin(k a) B sin(ka) − C cos(ka)
k cot(k a) (B sin(ka) − C cos(ka)) = B cos(ka) + C sin(ka) k k k cot(k a) sin(ka) − cos(ka) B = sin(ka) + cot(k a) cos(ka) C k k
We can now get the phase shift. tan δ = − C B
We need to use the boundary condition to get this phase shift. sin(ρ − ρ − cos(ρ − n → ρ j → and that our formula with the phase shift is R(r) ∝ = sin ρ −
π 2 π 2 ) π 2 )
+ δ (k)
ρ 1 π π cos δ sin(ρ − ) + sin δ cos(ρ − ) .227
V(r)
Scattering from a Spherical Well
E
a
r
V0
Matching the logarithmic derivative.
ρ=ka
Recalling that for r → ∞. we get k
dj (ρ) dρ
j (ρ)
=k
ρ=k a
(ρ) (ρ) B djdρ + C dndρ
Bj (ρ) + Cn (ρ)
. tan δ0 = − k cos(ka) sin(k a) − k cos(k a) sin(ka) C = B k sin(ka) sin(k a) + k cos(k a) cos(ka)
. ρ 2 2
we can identify the phase shift easily. For = 0.
log σ diffractive scattering
E
14.8
The Radial Equation for u(r) = rR(r) *
It is sometimes useful to use un (r) = rRn (r) to solve a radial equation problem. the diﬀerential scattering cross section is.228 With just the = 0 term. We do get the additional condition that u(0) = 0 to keep R normalizable. We can rewrite the equation for u. sin2 (δ ) dσ → dΩ k2 The cross section will have zeros when k = cot(ka) tan(k a) k k cot(k a) = k cot(ka).
.
There will be many solutions to this and the cross section will look like diﬀraction. d2 2 d + 2 dr r dr 2 1d u 1 = − 2 r dr2 r 1 d2 u(r) r dr2 u(r) d 1 du u 2 du 2u = − 2 + 2 − 3 r dr r dr r r dr r 2 1 du 2u du 2 du 2u 1d u − 2 + 3 + 2 − 3 = dr r dr r r dr r r dr2 2 2μ ( + 1)¯ u(r) h =0 + 2 E − V (r) − 2 2μr r h ¯ d2 u(r) 2μ ( + 1)¯ 2 h + 2 E − V (r) − u(r) = 0 2 2 dr 2μr h ¯
This now looks just like the one dimensional equation except the pseudo potential due to angular momentum has been added.
Now use the boundary condition at r = a to get one equation. Write down the form of the solution (in terms of known functions) in the two regions. outside o the well.229
For the case of a constant potential V0 . A particle has orbital angular momentum quantum number l = 1 and is bound in the potential well V (r) = −V0 for r < a and V (r) = 0 elsewhere. A particle has orbital angular momentum quantum number l = 1 and is bound in the potential well V (r) = −V0 for r < a and V (r) = 0 elsewhere. d) Find the transcendental equation which will determine the energy eigenvalues. Dividing by r to get R(ρ). 2. and the radial equation
d2 u(r) 2μ ( + 1)¯ 2 h + 2 E − V0 − u(r) = 0 2 2 dr 2μr h ¯ d2 u(r) ( + 1) + k 2 u(r) − u(r) = 0 2 dr r2 ( + 1) d2 u(ρ) − u(ρ) + u(ρ) = 0 dρ2 ρ2 For = 0. with some work. Write down the form of the solution (in terms of known functions) in the two regions. Do not bother to solve the equation. Your solution should satisfy constraints at the origin and at inﬁnity. Be sure to include angular dependence. 5. which is well behaved at at r = 0. Specify the relationship between the particles energy and any parameters in your solution. the solution of which will quantize the energies. Do not bother to solve the equation. the solution of which will quantize the energies. its easy to see that sin ρ and cos ρ are solutions. Be sure to include angular dependence. A particle of mass m with 0 total angular momentum is in a 3 dimensional potential well V (r) = −V0 for r < a (otherwise V (r) = 0).
. Use u(r) = rR(r) to simplify the calculation.
2μ(E−V0 ) h2 ¯
and ρ = kr. Now use the boundary condition at r = a to get one equation.9
Sample Test Problems
1. 3. we deﬁne k = becomes. c) Write down the boundary conditions that must be satisﬁed to match the two regions. Write down (but do not solve) the equation for the energies for = 1. Find the energies of the two lowest energy states for = 0.
14. to the time independent Schr¨dinger equation. 4. which has the right behavior as r → ∞. o inside the well. Your solution should satisfy constraints at the origin and at inﬁnity. we see that these are j0 and n0 . The solutions can be checked for other . a) Write down the form of the (l = 0) solution. Again specify how the parameters depend on energy. A particle is conﬁned to the inside of a sphere of radius a. b) Write down the form of the solution to the time independent Schr¨dinger equation.
φ)
We have already studied the spherical harmonics. ψn
m (r)
= Rn (r)Y
m (θ. d2 2 d + dr2 r dr RE (r) + 2μ h ¯2 E+ ( + 1)¯ 2 h Ze2 − r 2μr2 RE (r) = 0
where μ is the reduced mass of the nucleus and electron.1) using techniques similar to those used to solve the 1D harmonic oscillator equation. The radial wavefunction satisﬁes the diﬀerential equation that depends on the angular momentum quantum number .230
15
Hydrogen
The Hydrogen atom consists of an electron bound to a proton by the Coulomb potential. We ﬁnd the eigenenergies
E=−
1 2 2 2 Z α μc 2n2
and the radial wavefunctions
∞
Rn (ρ) = ρ
k=0
ak ρk e−ρ/2
where the coeﬃcients of the polynomials can be found from the recursion relation
ak+1 =
k+ +1−n ak (k + 1)(k + 2 + 2)
. V (r) = − Ze2 r
Since the potential is spherically symmetric.3. V (r) = − e2 r
We can generalize the potential to a nucleus of charge Ze without complication of the problem. μ= me mN me + mN
The diﬀerential equation can be solved (See section 15. the problem separates and the solutions will be a product of a radial wavefunction and one of the spherical harmonics.
2. n − 1 This unusual way of labeling the states comes about because a radial excitation has the same energy as an angular excitation for Hydrogen. 3.3.
15..n−1 ∝ rn−1 e−Zr/na0
. ..2) Here is a list of the ﬁrst several radial wave functions Rn (r). the total angular momentum quantum number = 0.231 and
ρ=
−8μE r.1
The Radial Wavefunction Solutions
Deﬁning the Bohr radius h ¯ . 1. plus 1.. This principle quantum number is actually the sum of the radial quantum number plus n = nr + + 1 and therefore. 2.. This is often referred to as an accidental degeneracy.. αmc we can compute the radial wave functions (See section 15. h ¯2
The principle quantum number n is an integer from 1 to inﬁnity.the largest
radial wavefunction is given by
Rn. n = 1. a0 = R10 R21 R20 R32 R31 R30 = 2 = 1 √ 3 Z a0
3 2
e−Zr/a0
3 2
Z 2a0
3
Zr a0
e−Zr/2a0 e−Zr/2a0
2
Z 2 Zr = 2 1− 2a0 2a0 √ 3 2 Z Zr 2 2 √ = 3a0 a0 27 5 √ 3 4 2 Z 2 Zr = 3 3a0 a0 = 2 Z 3a0
3 2
e−Zr/3a0 1− Zr 6a0 e−Zr/3a0 e−Zr/3a0
1−
2 (Zr)2 Zr + 3a0 27a2 0
For a given principle quantum number n. must be less than n. .
2: Compute the expected values of E. Again. and hence no nodes in the radial wavefunction. and Ly in the Hydrogen state √ 1 10ψ21−1 ). Lz .4.232 The radial wavefunctions should be normalized as below.* 6 (4ψ100 + 3ψ211 − iψ210 +
The pictures below depict the probability distributions in space for the Hydrogen wavefunctions. L2 .
. for a given n the maximum state has no radial excitation. we see more radial excitation.
The graphs below show the radial wave functions.
∞ ∗ r2 Rn Rn dr = 1 0
* See Example 15. As ell gets smaller for a ﬁxed n.
233
.
4.4.4.4: What is the expectation value of the radial component of velocity in the state
.234
A useful integral for Hydrogen atom calculations is.3: What is the expectation value of r in the state ψ100 ?*
* See Example 15.
∞
dx xn e−ax =
0
n! an+1
* See Example 15.2: What is the expectation value of
1 r
in the state ψ100 ?*
* See Example 15.
. i. these are ψ200 .. as depicted in the ﬁgures above and below. From there on follow the alphabet with g. = 1 states “p”. The convention is to name = 0 states “s”. The second excited state has n = 3 with the 3s. 3p and 3d states being degenerate. again not counting diﬀerent spin states. h.
The ground state of Hydrogen has n = 1 and = 0. ψ210 . The ﬁrst excited state of Hydrogen has n = 2. and = 3 states “f”. ψ211 . Remember. This totals 9 states with the diﬀerent allowed m values.2
The Hydrogen Spectrum
The ﬁgure shows the transitions between Hydrogen atom states. and ψ21−1 . = 2 states “d”. all values of < n are allowed. There are actually four degenerate states (not counting diﬀerent spin states) for n = 2. The Hydrogen spectrum was primarily investigated by measuring the energy of photons emitted in transitions between the states.. . This is conventionally called the 1s state. In general there are n2 degenerate states. In terms of ψn m .235 ψ100 ?*
15. These would be called the 2s and 2p states.
d2 2 d + 2 dr r dr RE (r) + 2μ h ¯2 E+ ( + 1)¯ 2 h Ze2 − 2 r 2μr RE (r) = 0
First we change to a dimensionless variable ρ.1
Derivations and Calculations
Solution of Hydrogen Radial Equation *
The diﬀerential equation we wish to solve is. 2E λ 1 − ρ 4 R = 0. as we will later learn.236
Transitions which change
by one unit are strongly preferred.3. −8μE r.
15. ρ= giving the diﬀerential equation ( + 1) d2 R 2 dR − + R+ 2 dρ ρ dρ ρ2 where the constant λ= Ze2 h ¯ −μ = Zα 2E −μc2 . h ¯2
.3
15.
We write G as a sum.
We plug the sum into the diﬀerential equation. R(ρ) = G(ρ)e
−ρ 2
We should also pick of the small r behavior. ρ2 ρ ρ s2 − s + 2s = ( + 1) s(s + 1) = ( + 1)
So either s =
or s = − − 1. d2 R 1 − R=0 dρ2 4 This can be solved by R = e
−ρ 2
. we get s(s − 1) R R R + 2s 2 − ( + 1) 2 = 0.237 Next we look at the equation for large r. ( + 1) d2 R 2 dR − + R=0 dρ2 ρ dρ ρ2 Assuming R = ρs .
−1 ∞
ak+1 ((k + + 1)(k + ) + 2(k + + 1) − ( + 1)) ρk+
k=−1
=
k=0
ak ((k + ) − (λ − 1)) ρk+
−1
.
∞ ∞
G(ρ) = ρ
k=0
ak ρk =
k=0
ak ρk+
The diﬀerential equation for G(ρ) is 2 d2 G − 1− dρ2 ρ dG + dρ λ−1 ( + 1) − ρ ρ2 G(ρ) = 0.
∞
ak (k + )(k + − 1)ρk+
k=0
−2
− (k + )ρk+
−1
−1
+ 2(k + )ρk+
−2
−2
+(λ − 1)ρk+
∞
− ( + 1)ρk+
=0
−2
ak ((k + )(k + − 1) + 2(k + ) − ( + 1)) ρk+
k=0 ∞
=
k=0
ak ((k + ) − (λ − 1)) ρk+
−1
Now we shift the sum so that each term contains ρk+
∞
−1
. The second is not well normalizable. so we explicitly include this.
so we can derive the recursion relation for the constants ak . We will call n the principal quantum number. ρ= −8μE r= h ¯2 2Z 4μ2 c2 Z 2 α2 2μcZα r= r= r 2 2 h ¯n na0 h ¯ n
15.2
Computing the Radial Wavefunctions *
The radial wavefunctions are given by
n− −1
R(ρ) = ρ
k=0
ak ρk e−ρ/2
. ak+1 ak = = = k+ +1−λ (k + + 1)(k + ) + 2(k + + 1) − ( + 1) k+ +1−λ k+ +1−λ = k(k + 2 + 1) + 2(k + + 1) k(k + 2 + 2) + (k + 2 + 2) 1 k+ +1−λ → (k + 1)(k + 2 + 2) k
This is then the power series for G(ρ) → ρ eρ unless it somehow terminates. since the energy will depend only on n. Plugging in for λ we get the energy eigenvalues.238 The coeﬃcient of each power of ρ must be zero. The number of nodes in G will be nr . (k + 1)(k + 2 + 2)
We can rewrite ρ. −μc2 = n.3. λ = nr + + 1 ≡ n.
The recursion relation is ak+1 =
k+ +1−n ak . 2E 1 E = − 2 Z 2 α2 μc2 2n Zα
The solutions are Rn (ρ) = ρ
∞ k=0
ak ρk e−ρ/2 . substituting the energy eigenvalue. We can terminate the series if for some value of k = nr .
0
k+ +1−n ak .239 where ρ=
2Z r na0
and the coeﬃcients come from the recursion relation ak+1 = The series terminates for k = n − − 1. Lets try R20 .
∞ ∗ r2 Rn Rn dr = 1 0 ∞
C2
0
r2 e−2Zr/a0 dr = 1
This can be integrated by parts twice. Lets start with R10 . (k + 1)(k + 2 + 2)
R10 (r) = ρ0
k=0
ak ρk e−ρ/2
R10 (r) = Ce−Zr/a0
We determine C from the normalization condition. No recursion is needed.
1
R20 (r) = ρ0
k=0
ak ρk e−ρ/2
R20 (r) = (a0 + a1 ρ)e−ρ/2
. a0 2 2Z
2 ∞
C
2 0
e−2Zr/a0 dr = 1 2 a0 2Z C2 =
3
C2 = 1 2Z a0 2Z a0
3
1 2
1 C= √ 2 R10 (r) = 2 Z a0
3 2
3 2
e−Zr/a0
R21 can be computed in a similar way.
6 (4ψ100 + 3ψ211 − iψ210 + First check the normalization.240 k+ +1−n ak (k + 1)(k + 2 + 2) 0+0+1−2 −1 a0 = a0 a1 = (0 + 1)(0 + 2(0) + 2) 2 Zr R20 (r) = C 1 − e−Zr/2a0 2a0 ak+1 = We again normalize to determine the constant. Find the expected value of the Energy. we can just square probability amplitudes to compute the expectation value of L2 . L2 . We must write Ly = (L+ − L− )/2i and compute. and Ly . The eigenvalues are ( + 1)¯ 2 . L2 .4. so we can easily compute expectation values of those operators. En E = = 1 1 − α2 μc2 2 2 n 1 1 1 1 1 21 7 1 2 2 16 11 + 9 22 + 1 22 + 10 22 2 = − α2 μc2 = − α2 μc2 − α μc 2 36 2 36 2 12
Similarly.
15.1
Examples
Expectation Values in Hydrogen States
An electron in the Coulomb ﬁeld of a proton is in the state described by the wave function √ 1 10ψ21−1 ). Ly = = √ √ 1 4ψ100 + 3ψ211 − iψ210 + 10ψ21−1 L+ − L− 4ψ100 + 3ψ211 − iψ210 + 10ψ21−1 72i √ √ 1 4ψ100 + 3ψ211 − iψ210 + 10ψ21−1  − 3L− ψ211 − i(L+ − L− )ψ210 + 10L+ ψ21−1 72i
. and Lz . Lz . √ 36 42 + 32 +  − i2 +  102 = =1 36 36
The terms are eigenstates of E. h ¯ Lz = h −1 16(0) + 9(1) + 1(0) + 10(−1) = h ¯ 36 36
Computing the expectation value of Ly is harder because the states are not eigenstates of Ly . h L 2 = h2 ¯ 10 2 16(0) + 9(2) + 1(2) + 10(2) = h ¯ 36 9
The Eigenvalues of Lz are m¯ .4
15.
there is no angular dependence to the wavefunction so no velocity except in the radial direction.4.4. ψ100  − αmc Ze2 Z 2 e2 ψ100 = − = −Z 2 α2 mc2 = 2E100 = Z 2 e2 r a0 h ¯
15.4. We can ﬁnd the term for
p2 r 2m
in the radial equation.4
The Expectation Value of vr in the Ground State
For = 0.2
The Expectation of
1 r
in the Ground State
R10 1 ψ100  ψ100 r
∞
= 2 =
Z a0
3 2
e−Zr/a0
∞
∗ Y00 Y00
dΩ
0 ∞
1 ∗ r2 R10 R10 dr r Z a0
3
=
0
∗ rR10 R10 dr
= 4 = Z a0
Z a0
3
re−2Zr/a0 dr = 4
0
a0 2Z
2
1!
We can compute the expectation value of the potential energy. So it makes sense to compute the radial component of the velocity which is the full velocity.3
The Expectation Value of r in the Ground State
∞
ψ100 rψ100 =
0
r
3
∗ R10 R10
dr = 4
Z a0
3
∞
r3 e−2Zr/a0 dr = 3!
0
3 a0 1 a0 = 4Z 2Z
15.241 √ √ √ √ √ √ h ¯ 4ψ100 + 3ψ211 − iψ210 + 10ψ21−1  − 3 2ψ210 − i 2ψ211 + i 2ψ21−1 + 10 2ψ210 72i √ √ √ 2¯ h 4ψ100 + 3ψ211 − iψ210 + 10ψ21−1  − 3ψ210 − iψ211 + iψ21−1 + 10ψ210 72i √ √ √ √ √ √ √ (2 5 − 3 2)¯ 2¯ h h h (−6 + 2 10)i 2¯ (−3i − 3i + 10i + 10i) = = 72i 72i 36
= = =
15.
∞ ∗ r2 R10 0
ψ100 (vr ) ψ100
2
=
−¯ 2 h m2
2 d d2 + dr2 r dr
R10 dr
.
) The energies of the states are En = − 13. ψ211 .6 eV.6 For the n = 1 ﬁnal state.6 eV. Answer The n = 4 state can decay into states with n = 1. Find the diﬀerence in wavelength between light emitted from the 3P → 2S transition in Hydrogen and light from the same transition in Deuterium.
1 1 − 2 n2 4
2. ψ310 .
. 2. ψ321 .5
Sample Test Problems
1. The atom decays to a lower state by emitting a photon. ψ300 . = 2). ψ31−1 . list all the n = 1.7 eV. 3 hydrogen states. (Deuterium is an isotope of Hydrogen with a proton and a neutron in the nucleus. E = For the n = 3 ﬁnal state. the RMS velocity is αc or
We can compute the expected value of the kinetic energy. E = For the n = 2 ﬁnal state. ψ322 .6 = 2. E =
15 16 13. K.242
3 ∞
=
−¯ 2 h 4 m2 −¯ h 4 m2
2
Z a0 Z a0 Z a0
2
r2 e
0 3
−Zr a0
Z2 2Z 2 − a r a0 0
3
e a0 2Z
−Zr a0
dr
= =
Z2 a0 2 a2 2Z 0
−
2Z a0
2
h ¯2 m2
Since a0 =
h ¯ αmc . ψ21−1 .E. 3. (Really the n = 1 state will be suppressed due to selection rules but this is supposed to be a simple question.6 = 0.8 eV. ψ210 .
15. Eγ = 13. Using the ψn m notation. Find the possible photon energies that may be observed. (Neglect the existence of spin. ψ32−1 . ψ200 . n2
The photon energy is given by the energy diﬀerence between the states. 3 16 13. 7 144 13. ψ32−2 .) Get a numerical answer. ψ100 . Give your answers in eV.) Answer The states are. = 1 h ¯2 Z2 1 mv 2 = = Z 2 α2 mc2 = −E100 2 2m a2 2 0
This is what we expect from the Virial theorem. 3. 2. ψ320 . ψ311 . A Hydrogen atom is in its 4D state (n = 4.6 = 12.
we get ψ100 (vr )2 ψ100 = Z 2 α2 c2 β=α= 1 137
For Z = 1.
Tritium is an isotope of hydrogen having 1 proton and 2 neutrons in the nucleus. Find the expected value of the potential r energy for this state. Find the possible photon energies that may be observed. It is possible to make a hydrogenlike atom from a proton and a muon. The atomic electron is undisturbed by this decay process and therefore ﬁnds itself in exactly the same state immediately after the decay as before it. l = 2). An electron in the Coulomb ﬁeld of a proton is in the state described by the wave function √ 1 10ψ21−1 ). Find the possible photon energies that may be observed. The atom decays to a lower state by emitting a photon. Give your answers in eV . 11. 8. θ. Calculate the expected
1 h h h 1 h ψ(t) = √ (ψ100 e−iE1 t/¯ − ψ200 e−iE2 t/¯ ) = e−iE1 t/¯ √ (ψ100 − ψ200 ei(E1 −E2 )t/¯ ) 2 2 ψrψ = 1 h h ψ100 − ψ200 ei(E1 −E2 )t/¯ rψ100 − ψ200 ei(E1 −E2 )t/¯ 2
. Now 6 (4ψ100 + 3ψ211 − ψ210 + ﬁnd the expected value of Ly .
10. Find the expected value of Lx . A Hydrogen atom is in its 3D state (n = 3. 13. Answer
1 √ (ψ100 2
− ψ200 ). A Hydrogen atom is in the state: 1 ψ(r) = √ (ψ100 + 2ψ211 − ψ322 − 2iψ310 + 2iψ300 − 4ψ433 ) 30
Z For the Hydrogen eigenstates. Give your answers in eV . * Write out the (normalized) hydrogen energy eigenstate ψ311 (r. The force binding the muon to the proton is identical to that for the electron but the muon has a mass of 106 MeV/c2 . φ). (Deuterium is an isotope of Hydrogen with a proton and a neutron in the nucleus. 6. L2 and Lz .51 MeV/c2 . Write down the wave function of the hydrogen atom state ψ321 (r). 12. l = 2). Find the expected value of Lz . Find the diﬀerence in frequency between light emitted from the 2P → 1S transition in Hydrogen and light from the same transition in Deuterium.) 14. The nucleus is unstable and decays by changing one of the neutrons into a proton with the emission of a positron and a neutrino. b) What is the“Bohr Radius” of the ground state of muonic hydrogen. The hydrogen atom is made up of a proton and an electron bound together by the Coulomb force. 9. compute the probability to ﬁnd the electron in the ground state of the new atom with Z=2. If the electron started oﬀ in the ψ200 (n = 2. The atom decays to a lower state by emitting a photon. ψnlm  1 ψnlm = a0 n2 . At t = 0 a hydrogen atom is in the state ψ(t = 0) = value of r as a function of time. a) What is the ground state energy of muonic hydrogen (in eV). A hydrogen atom is in the state: ψ(r) = √1 (ψ322 + 2ψ221 + 2iψ220 + ψ11−1 ) Find the possible 10 measured energies and the probabilities of each. A Hydrogen atom is in its 4D state (n = 4. l = 0) state of tritium. Calculate the expected value of r in the Hydrogen state ψ200 . Find the expected value of the Energy.243 4. The electron has a mass of 0. 7. 5. 15.
All the terms of the wavefunction contain a Y00 and r does not depend on angles. 1 a0
3 2
R10 R20 ψrψ
= 2 = = − = 1 √ 2
e−r/a0
3 2
1 a0
∞
1−
r 2A0 1 2
e−r/2a0 1− r2 r + 2 a0 4a0 e−r/a0 r3 dr
1 2a3 0
4e−2r/a0 +
0
√ r 2 2 1− 2a0 1 2a3 0
∞
e−3r/2a0 cos
E2 − E1 t h ¯
4r3 e
0
−2r a0
−r −r 1 1 4 −r 1 + r3 e a0 − r e a0 + 2 r5 e a0 2 2a0 8a0
+ = +
√ −3r −2 2r3 e 2a0 + 1 a0 3 24 2a0 2 √ −2 26 a0 2 a0 2
4
√
2
a0
r4 e 2a0
−3r
cos
E2 − E1 t h ¯
dr
+ 3a4 − 0
4
2a0 3
√ 2 + 24 a0
1 1 24a5 + 2 120a5 0 0 2a0 8a0 2a0 3
5
cos
E2 − E1 t h ¯
= =
3 + 3 − 12 + 15 + 2
= a0
3 + 3 − 12 + 15 + 2 √ E2 − E1 15 32 2 + cos t 4 81 h ¯
√ √ 16 E2 − E1 2 32 −12 2 + cos t 24 81 a0 243 h ¯ √ √ 64 256 2 E2 − E1 − 2 + cos t 27 81 h ¯
. so the angular integral just gives 1.244 The angular part of the integral can be done. 1 ψrψ = 2
∞ h h (R10 − R20 e−i(E2 −E1 )t/¯ )∗ r(R10 − R20 e−i(E2 −E1 )t/¯ )r2 dr 0
The cross terms are not zero because of the r. 1 ψrψ = 2
∞ 2 2 h h R10 + R20 − R10 R20 ei(E2 −E1 )t/¯ + e−i(E2 −E1 )t/¯ 0
r3 dr
1 ψrψ = 2
∞ 2 2 R10 + R20 − 2R10 R20 cos 0
E2 − E1 t h ¯
r3 dr
Now we will need to put in the actual radial wavefunctions.
ρ h ¯ μω = 0 = 0 1 2 2 μω r .245
16
3D Symmetric HO in Spherical Coordinates *
We have already solved the problem of a 3D harmonic oscillator by separation of variables in Cartesian coordinates (See section 12.
/2
Also. 2
Write the equation in terms of the dimensionless variable y ρ r d dr d2 dr2 = =
= ρy dy d 1 d = = dr dy ρ dy 1 d = ρ2 dy 2
Plugging these into the radial equation. d2 R 2 dR ( + 1) − + R=0 dy 2 y dy y2 R ≈ ys s(s − 1)y s−2 + 2sy s−2 = ( + 1)y s−2 s(s + 1) = ( + 1) R≈y
. ﬁnd the behavior for small y.2). The potential is V (r) = Our radial equation is d2 2 d + 2 dr r dr 2μ ( + 1)¯ 2 h E − V (r) − RE (r) 2 2 2μr h ¯ ( + 1) 2μE d2 R 2 dR μ2 ω 2 2 − 2 r R− + R+ 2 R 2 2 dr r dr r h ¯ h ¯ RE (r) + r . It is instructive to solve the same problem in spherical coordinates and compare the results. we get 1 d2 R 1 1 2 dR 1 ( + 1) 2μE − 4 ρ2 y 2 R − 2 + 2 R+ 2 R ρ2 dy 2 ρ y dy ρ ρ y2 h ¯ 2 d R 2 dR ( + 1) 2E − y2R − R + R+ dy 2 y dy y2 h ¯ω Now ﬁnd the behavior for large y. d2 R − y2R = 0 dy 2 R ≈ e−y
2
= =
0 0.
∞
R=y
k=0
ak y k e−y
2
∞ /2
=
k=0
ak y
+k −y 2 /2
e
We’ll need to compute the derivatives. dR = dy d R = dy 2
2 ∞ ∞
ak [( + k)y
k=0
+k−1
−y
+k+1
]e−y
2
/2
ak [( + k)( + k − 1)y
k=0
+k−2
− ( + k)y
+k+2
+k
−( + k + 1)y d2 R = dy 2
∞
+k
+y
]e−y
2
/2
ak [( + k)( + k − 1)y
k=0 +k
+k−2
−(2 + 2k + 1)y
+y
+k+2
]e−y
2
/2
We can now plug these into the radial equation. We can also run a single sum
ak ( + k)( + k − 1)y
k=0
+k−2
− (2 + 2k + 1)y
+k−2
+k
+y
+k
+k+2
+2( + k)y
+k−2
− 2y
+k
−y
+k+2
− ( + 1)y
+
2E y h ¯ω
=0
The terms for large y which go like y should cancel if we did our job right. so we can factor that out.246 Explicitly put in this behavior and use a power series expansion to solve the full equation.
∞
+k+2
and some of the terms for small y which go like y
+k−2
ak [( + k)( + k − 1) − ( + 1) + 2( + k)]y
k=0
+k−2
+
∞
2E − 2 − (2 + 2k + 1) y h ¯ω
+k
=0
+k−2
ak [ ( − 1) + k(2 + k − 1) − ( + 1) + 2 + 2k]y
k=0
+
∞
2E − 2 − (2 + 2k + 1) y h ¯ω + 2E − (2 + 2k + 3) y h ¯ω
+k
=0 =0
ak [k(2 + k + 1)]y
k=0
+k−2
+k
. ( + 1) 2E d2 R 2 dR − y2R − R=0 + R+ 2 2 dy y dy y h ¯ω Each term will contain the exponential e−y over all the terms.
∞
2
/2
.
we make the substitutions nr → 2nr and k → 2k in the recursion relation for ak+1 in terms of ak . the coeﬃcient for each power of y must be zero for this sum to be zero for all y.. as we will see from the recursion relation. Now we will do the usual shift of the ﬁrst term of the sum so that everything has a y k →k+2 2E − (2 + 2k + 3) y +k = 0 h ¯ω
+k
in it. The ﬁrst term in the sum runs the risk of giving us a power of y which cannot be canceled by the second term if k < 2. 2. k
Which will cause the wave function to diverge.247 Now as usual. by requiring 2E − (2 + 2nr + 3) = 0 h ¯ω 3 E = nr + + h ¯ω 2 These are the same energies as we found in Cartesian coordinates.
. ak+2 ≈ 2 ak . For k = 1 the term is (2 + 2)y −1 which cannot be made zero unless a1 = 0. This indicates that all the odd terms in the sum will be zero.. 4. Lets plug this back into the recursion relation.. ak+2 = − (2 + 2nr + 3) − (2 + 2k + 3) ak (k + 2)(2 + k + 3) 2(k − nr ) ak ak+2 = (k + 2)(2 + k + 3)
To rewrite the series in terms of y 2 and let k take on every integer value. there is no problem because the term is zero. we must examine the ﬁrst few terms of this sum to learn about conditions on a0 and a1 .
∞
ak+2 (k + 2)(2 + k + 3)y
k=0
+k
+ ak
ak+2 (k + 2)(2 + k + 3) + ak
2E − (2 + 2k + 3) = 0 h ¯ω 2E ak+2 (k + 2)(2 + k + 3) = −ak − (2 + 2k + 3) h ¯ω
2E ¯ − (2 + 2k + 3) ak+2 = − hω ak (k + 2)(2 + k + 3)
For large k. For k = 0. Before shifting terms. We must terminate the series for some k = nr = 0.
03 20. If we were more industrious. and for separation in Cartesian coordinates. Remember that there are 2 + 1 states with diﬀerent z components of angular momentum for the spherical coordinate states. 02 11. 111 004(3).
. 211(3)
NSpherical 1 3 6 10 15
NCartesian 1 3 6 10 15
The number of states at each energy matches exactly. Remember that the parity is (−1) for the angular momentum states and that it is (−1)nx +ny +nz for the Cartesian states. 04
nx ny nz 000 001(3 perm) 002(3 perm). E
3 h 2 ¯ω 5 h 2 ¯ω 7 h 2 ¯ω 9 h 2 ¯ω 11 h 2 ¯ω
nr 00 01 10. 310(6). 011(3 perm) 003(3 perm). we could verify that the wavefunctions in spherical coordinates are just linear combinations of the solutions in Cartesian coordinates.248
ak+1 =
(k − nr ) ak (k + 1)( + k + 3/2)
∞
Rnr =
k=0
ak y
+2k −y 2 /2
e
E=
2nr + +
3 2
h ¯ω
The table shows the quantum numbers for the states of each energy for our separation in spherical coordinates. The parities of the states also match. 220(3). 210(6 perm). 12.
⎟ ⎠⎝ ⎠ ψj .. ψi ≡ ui ψ ψ =
i
ψi ui
The wavefunctions are therefore represented as vectors.. ˆ ui uj = δij Deﬁne the components of a state vector ψ (analogous to xi )..1
The Matrix Representation of Operators and Wavefunctions
We will deﬁne our vectors and matrices using a complete set of. . orthonormal basis states (See Section7. ⎟ ⎜ ψ2 ⎟ ⎟⎜ ⎟ ...
17.. ⎝ ⎠ ⎝ Oi1 Oi2 (Oψ)i . in CohenTannoudji et al.. usually the set of eigenfunctions of a Hermitian operator.... These topics are covered at very diﬀerent levels in Gasiorowicz Chapter 14. Chapters II. These basis states are analogous to the orthonormal unit vectors in Euclidean space xi .. . O1j .
k
Similarly. To include the spin of electrons and nuclei in our discussion of atomic energy levels... Oψ = Oψ = O
j
ψj uj =
j
ψj Ouj
If we dot ui  into this equation from the left. we get (Oψ)i = ui Oψ =
j
ψj ui Ouj =
j
Oij ψj
This is exactly the formula for a state vector equals a ⎛ ⎞ ⎛ O11 O12 (Oψ)1 (Oψ)2 ⎟ ⎜ O21 O22 ⎜ ⎜ ⎟ ⎜ .. ⎟ = ⎜ .... Oij . Deﬁne the matrix element Oij ≡ ui Ouj ... .. Griﬃths Chapters 3... we can look at the product of two operators (using the identity (OP )ij = ui OP uj =
k
ui Ouk uk P uj =
k
Oik Pkj
....... we will need the matrix representation. .. .. O2j .. . ⎜ . Since the eigenfunctions of Hermitian operators are orthogonal (and we normalize them) we can now use the standard linear algebra to solve quantum problems with vectors and matrices. uk uk  = 1). .1) ui ... ⎟ ⎜ .. ⎞⎛ ⎞ ψ1 . .. more rigorously. ... 4 and..249
17
Operators Matrices and Spin
We have already solved many problems in Quantum Mechanics using wavefunctions and diﬀerential operators. IV and IX. We know that an operator acting on a wavefunction gives a wavefunction...
matrix operator times a state vector.
* See Example 17.. (OP )1j ⎜ (OP )21 (OP )22 . ⎟ ⎜ P21 P22 ⎜ ⎟⎜ . ⎟ ⎟ .*
Now compute the matrix for the Hermitian Conjugate (See Section7. (OP )ij .
⎞ .. ... .
So..... Check that this is true for A and A† . . ⎟ ⎠ . ..... ⎟ = ⎠ . .. P1j .. ⎛ ⎞ ..
17. ...10. Pi1 Pi2 ... ....250 This is exactly the formula for the product of two matrices.. (O† )ij = ui O† uj = Oui uj = uj Oui
∗ ∗ = Oji
The Hermitian Conjugate matrix is the (complex) conjugate transpose.. .... .. . ⎜ ... If ψ = ψj uj and φ = φk uk then..1: The Harmonic Oscillator Hamiltonian Matrix.... The both represent the same state but are diﬀerent mathematical objects.. ⎝ (OP )i1 (OP )i2 ... . Pij . .... ..k j..2: The harmonic oscillator raising operator. ⎝ ⎠⎝ Oi1 Oi2 .. P2j . P11 P12 ⎜ O21 O22 .1) Assume we have an atomic state with = 1 (ﬁxed) but m free. O2j ... This becomes explicit in the matrix representation....2) of an operator.. (OP )2j ⎜ .. ⎟ ⎜ . ⎟ ⎟ ...... We may use the eigenstates
...... .3: The harmonic oscillator lowering operator.. .10. .. Oij ..........* * See Example 17..... ⎜ .
(OP )11 (OP )12 . the dot product is
j k ∗ ψj φk uj uk = j. all in the space of orthonormal functions. .
ψφ =
We can write this in dot product in matrix notation as
∗ ψφ = ( ψ1 ∗ ψ2 ∗ ψ3
⎞ φ1 ⎜φ ⎟ .* * See Example 17. ....... .. O1j . ..
⎛
The bra vector is the conjugate transpose of the ket vector.... ) ⎝ 2 ⎠ φ3 . .....10. ⎛ ⎞⎛ O11 O12 . wave functions are represented by vectors and operators by matrices..
We know that there is a diﬀerence between a bra vector and a ket vector.. ...k ∗ ψj φk δjk = k ∗ ψk φk .. ..2
The Angular Momentum Matrices*
An important case of the use of the matrix form of operators is that of Angular Momentum (See Section13.....
That is.2) Since these matrices represent physical variables. Ignoring the (ﬁxed) radial part of the wavefunction.11.11. Ly ] = i¯ Lz h We verify this with an explicit computation of the commutator. We can easily derive (see section 17.3
Eigenvalue Problems with Matrices
It is often convenient to solve eigenvalue problems like Aψ = aψ using matrices. number of states. for example. they are equal to their conjugate transpose. ⎛ ⎞⎛ ⎞ 0 1 0 ψ1 h ¯ ⎝ ∗ ∗ ∗ ψLx ψ = ( ψ1 ψ2 ψ3 ) √ 1 0 1 ⎠ ⎝ ψ2 ⎠ 2 0 1 0 ψ3 ⎞ ⎛ ψ2 h ¯ ∗ ∗ ∗ = √ ( ψ1 ψ2 ψ3 ) ⎝ ψ1 + ψ3 ⎠ 2 ψ
2
=
h ¯ ∗ ∗ ∗ √ (ψ1 ψ2 + ψ2 (ψ1 + ψ3 ) + ψ3 ψ2 ) 2
17. let’s compute an expectation value of Lx in the matrix representation for the general state ψ.1) the matrices representing the angular momentum operators for = 1. (see section 17. then ﬁnding the linear combinations which are the energy eigenstates. is just the numerical coeﬃcient of the eigenstate. We will write our 3 component vectors like ⎞ ψ+ ψ = ⎝ ψ0 ⎠ . ⎛ 0 1 h ¯ ⎝ 1 0 Lx = √ 2 0 1 ⎞ 0 1⎠ 0 ⎛ ⎞ 0 1 0 h ¯ ⎝ Ly = √ −1 0 1 ⎠ 2i 0 −1 0 ⎛ ⎞ 0 0 ⎠ −1 ⎛
1 0 Lz = h ⎝ 0 0 ¯ 0 0
(1)
The matrices must satisfy the same commutation relations as the diﬀerential operators. manageable. we expect them to be Hermitian.251 of Lz as a basis for our states and operators. As an example of the use of these matrices. our state vectors for = 1 must be a linear combination of the Y1m ψ = ψ+ Y11 + ψ0 Y10 + ψ− Y11 where ψ+ . The calculation is simple in principle but large dimension matrices are diﬃcult to work with by hand. ψ− The angular momentum operators are therefore 3X3 matrices. Note that they are also traceless. Many problems in Quantum Mechanics are solved by limiting the calculation to a ﬁnite. Standard computer utilities are readily
. [Lx .
. ⎟ ⎜ ψ2 ⎟ ⎠ ⎝ ⎠ = 0....
Subtracting the right hand side of the equation.
We can check whether the eigenvectors are orthogonal..... ⎟ ⎜ ψ2 ⎟ ⎜ ψ2 ⎟ ⎠⎝ ⎠ = a⎝ ⎠ . h
(x) −1 2
2 1
These vectors. ψ3 ψ3 .. =0 A31 A32 A33 − a . and any
= 1 vectors. 0... ..10... A13 A23 A33 − a .
* See Example 17.. ψ1 ψ1 .. the determinant of the matrix must be zero. if a particle is in a angular momentum state χ and the angular momentum in the x direction is measured..*
The eigenvectors computed in the above example show that the x axis is not really any diﬀerent than the z axis.. For example. ⎛ ψ0¯ ψ+¯ = h h
1 ∗ √ 2 1 − √2 ∗
0
⎝
1 2 1 √ 2 1 2
⎞ ⎠=0
The others will also prove orthogonal. . The eigenvalues are +¯ ... . ... A21 A22 − a A23 . A12 A22 − a A32 . . ⎞⎛ ⎞ .. Should ψ+¯ and ψ−¯ be orthogonal? h h NO...252 available to help solve this problem. the same as for z.4: Eigenvectors of Lx . ψ1 . A11 − a A12 A13 .. . They are eigenvectors of diﬀerent hermitian operators... A13 A23 A33 .. ... The eigenvectors may be used to compute the probability or amplitude of a particular measurement..... and −¯ .. ⎞⎛ ⎞ ⎛ ⎞ .. ..... the probability to measure +¯ is h P+¯ = h ψ+¯ χ h
(x) 2 (x) (z)
. We solve this equation to get the eigenvalues. as they must be.
For the product to be zero. we have ⎛ A11 − a ⎜ A21 ⎝ A31 . ψ3 .. The normalized eigenvectors of h h Lx are ⎛ 1 ⎞ ⎛ 1 ⎞ ⎛ −1 ⎞ ψ+¯ = ⎝ √2 ⎠ h
(x) 1 2 2 1 √ (x) ψ0¯ = ⎝ 0 ⎠ h 1 − √2 2
ψ−¯ = ⎝ √2 ⎠ .. A12 A22 A32 .... can be written in terms of the eigenvectors of Sz .. ⎛ A11 ⎜ A21 ⎝ A31 ..
* * See Example 17.
. For now. * See Example 17.4
An
= 1 System in a Magnetic Field*
We will derive the Hamiltonian terms added when an atom is put in a magnetic ﬁeld in section 19. H = −μ · B If the magnetic ﬁeld has a gradient in the z direction. then the magnetic moment term in the Hamiltonian becomes ⎛ ⎞ 1 0 0 μB B H= Lz = μB B ⎝ 0 0 0 ⎠ . 0.*
17.6: The energy eigenstates of an = 1 system in a Bﬁeld.10.8: Time development of a state in a B ﬁeld.10. A magnetic moment is associated with angular momentum. we can be satisﬁed with the classical explanation that the circulating current associated with nonzero angular momentum generates a magnetic moment. the magnetic moment is μ= −e L.5
Splitting the Eigenstates with SternGerlach
A beam of atoms can be split into the eigenstates of Lz with a SternGerlach apparatus. This magnetic moment has the same interaction as in classical EM. 2mc
For the electron mass. μB = e¯ h . F =− ∂U ∂B = μz ∂z ∂z
A magnet with a strong gradient to the ﬁeld is shown below.253
17. there is a force exerted (classically). and −μB B. in normal atoms. For the orbital angular momentum in a normal atom. adding a term to the Hamiltonian. μ= L −e L = μB 2mc h ¯
This magnetic moment interacts with an external ﬁeld. the magnitude of μ is one Bohr magneton. h ¯ 0 0 −1 So the eigenstates of this magnetic interaction are the eigenstates of Lz and the energy eigenvalues are +μB B. 2me c
If we choose the direction of B to be the z direction. H = −μ · B. as does a classical current loop.
254
Gradient in Bfield
S N
Lets assume the ﬁeld gradient is in the z direction. If we put them through another SternGerlach apparatus. = 1 beam of atoms will be split into the three beams (of equal intensity) corresponding to the diﬀerent eigenvalues of Lz . We can make a fancy SternGerlach apparatus which puts the beam back together as shown below.
S
N
S
N
S
N
⎧ ⎫ ⎨+⎬ → 0 ⎩ ⎭ − z
We can represent the apparatus by the symbol to the right.
. a beam of atoms (assume = 1) is sent into a magnet with a strong ﬁeld gradient. The atoms come from an oven through some collimator to form a beam. Similarly for the middle beam in the m = 0 state and the lower beam in the m = −1 state. they will all go into the top beam again. In the SternGerlach experiment. The beam is said to be unpolarized since the three m states are equally likely no particular state has been prepared. An unpolarized.
l=1 atomic beam
S N
m=1 m=0 m=1
The atoms in the top beam are in the m = 1 state.
An apparatus which blocks both the + and . The apparatus below picks out the m = 1 state
S
N
S
N
⎧ ⎫ ⎨+⎬ → 0 ⎩ ⎭ − z again representing the apparatus by the symbol at the right.255 We can use this apparatus to prepare an eigenstate. an apparatus with no blocking could be written as the sum of the three projection operators. . the apparatus would be represented by ⎧ ⎫ ⎨ + ⎬ 0 →= 0 0 + − −. We could also represent our apparatus plus blocking by an operator O = + + where we are writing the states according to the m value. ⎧ ⎫ +1 ⎨+⎬ →= + + + 0 0 + − − = zm zm  = 1 0 ⎩ ⎭ m=−1 − z If we block only the m = 1 beam. or 0. ⎩ ⎭ − z
. This is a projection operator onto the + state. either +.beams
S
N
S
N
S
N
⎧ ⎫ ⎨ + ⎬ → 0 ⎩ ⎭ − z would be represented by the projection operator O = 0 0
S
N
Similarly.
7: A series of SternGerlachs.4) of the operator for rotations about the zaxis gives ⎞ ⎛ iθ 0 e z 0 Rz (θz ) = ⎝ 0 1 0 ⎠.*
.5: A 90 degree rotation about the z axis. vectors. Rx (θx ) = Ry (θy ) =
h eiθx Lx /¯ h eiθy Ly /¯
The above formulas for the rotation operators must apply in both the matrix representation and in the diﬀerential operator representation. tensors. For a rotation of π radians. Operators which preserve dot products are called unitary. rotations about the other axes follow the same form.11. We could choose any other direction to deﬁne our basis states. like dot products of state vectors. We can derive (see section 17..10. 2 1 1 (1 − cos(θy )) − √2 sin(θy ) 1 (1 + cos(θy )) 2 2 Try calculating the rotation operator for the xaxis yourself. Experience has shown that knowing how an object transforms under rotations is important in classifying the object: scalars. * See Example 17.*
17. Rz (θz ) = ψ =
h eiθz Lz /¯ Rz (θz )ψ
Since there is nothing special about the zaxis.11.256 * See Example 17.11.10. A computation (see section 17. Ry interchanges the plus and minus components (and changes the sign of the zero component). This operator transforms an angular momentum state vector into an angular momentum state vector in the rotated system.3) the operator for rotations about the zaxis. We proved that operators of the above form.5) of the operator for rotations about the yaxis yields ⎞ ⎛1 1 1 √ sin(θy ) 2 (1 + cos(θy )) 2 (1 − cos(θy )) 2 ⎟ ⎜ 1 1 √ sin(θy ) cos(θy ) Ry (θy ) = ⎝ − √2 sin(θy ) ⎠.. Redeﬁning the coordinate axes cannot change any scalars. −iθz 0 0 e A computation (see section 17. the states here are of a new type and are referred to as spinors. (with hermitian matrices in the exponent) are unitary.6
Rotation operators for
=1 *
We have chosen the z axis arbitrarily. Hence. which is consistent with what we expect. Note also that the above rotation matrices are quite diﬀerent than the ones used to transform vectors and tensors in normal Euclidean space. We wish to know how to transform from one coordinate system to another.
Note that both of the above rotation matrices reduce to the identity matrix for rotations of 2π radians.
I+ = 1 (1 + cos(θy ))2 4 I0 = 1 sin2 (θy ) 2 I− = 1 (1 − cos(θy ))2 4
These add up to 1. Now we rotate to a new (primed) set of basis states 0 with the z along the u direction. ˆ An alternate solution would be to use the Lu = u · L = cos θLz + sin θLx operator. Some particles.7
A Rotated SternGerlach Apparatus*
Imagine a SternGerlach apparatus that ﬁrst separates an = 1 atomic beam with a strong Bﬁeld gradient in the zdirection. we ﬁrst determine the state after the ﬁrst apparatus.
. leaving only the eigenstate of Lz with eigenvalue +¯ . The intensity in the + beam is then I+ =  ψ+ ψ+ 2 .257
17. neutrinos. ⎧ ⎫ ⎧ ⎫ ⎨ + D+ ⎬ ⎨+⎬ → 0 D0 Oven → 0 ⎩ ⎭ ⎩ ⎭ − D− u − z We put a detector in each of the beams split in u to determine the intensity. also called spin. it doesn’t matter. We follow this with h an apparatus which separates in the udirection. Let’s assume the beam has atoms moving in the ydirection. This means a rotation through an angle θ about the y direction. What fraction of the (remaining) beam will go into each of the three beams which are split in the udirection? We could represent this problem with the following diagram. y. if we only need to know the intensities.4.8
Spin
Earlier. It ⎛ the 1 (z) is just ψ+ = ⎝ 0 ⎠ with the usual basis. like ψ+ . which is at an angle θ from the zdirection. The apparatus blocks two separated beams. but still perpendicular to the direction of travel of the beam. and quarks have half integer internal angular momentum. Find the eigenvectors (u) (u) (z) of this operator. So the state coming out of the second apparatus is ⎞⎛ ⎞ ⎛1 1 1 √ sin(θy ) 2 (1 + cos(θy )) 2 (1 − cos(θy )) 1 2 ⎟⎝ ⎠ ⎜ (z) 1 1 √ sin(θy ) cos(θy ) = ⎝ − √2 sin(θy ) Ry (θ)ψ+ ⎠ 0 2 1 1 1 0 √ 2 (1 − cos(θy )) − 2 sin(θy ) 2 (1 + cos(θy )) ⎛1 ⎞ 2 (1 + cos(θy )) 1 = ⎝ − √ sin(θy ) ⎠
1 2 (1
− cos(θy ))
2
The 3 amplitudes in this vector just need to be (absolute) squared to get the 3 intensities. we showed that both integer and half integer angular momentum could satisfy (See section 13. To solve this with ⎞ rotation matrices. There are no coordinates θ 2 and φ associated with internal angular momentum so the only thing we have is our spinor representation. but. The problem didn’t clearly deﬁne whether it is +θ or −θ.
1 2
17. We will now develop a spinor representation for spin 1 .5) the commutation relations for angular momentum operators but that there is no single valued functional representation for the half integer type. like electrons.
6) the matrix operators for spin. Sy ] = = h ¯2 4 h ¯2 4 0 1 i 0 1 0 0 −i −i − 0 −i 0 − 0 i 0 i 0 i −i 0 h ¯2 = 2 0 1 1 0 h ¯ i 0 = i¯ h 0 −i 2
1 0 0 −1
= i¯ Sz h
The spin operators are an (axial) vector of matrices.258 Electrons. To form the spin operator for an arbitrary direction u. There are no spin 3/2 electrons so there are only two possible spin states for an electron. for example. have total spin one half. [Sx . σj } = 2δij = −σz σx σz σy = −σy σz
. It is easy to derive (see section 17. The − 1 ¯ eigenstate amplitude is in 2h the lower component. we simply dot the unit vector into the vector of matrices. that the eigenvalues of Sz are + 2 ¯ and − 2 ¯ . χ= with the normalization condition that a2 + b2 = 1. The usual basis states are the eigenstates of Sz . Sx = h ¯ 2 0 1 1 0 Sy = h ¯ 2 0 i −i 0 Sz = h ¯ 2 1 0 0 −1 a b
These satisfy the usual commutation relations from which we derived the properties of angular momentum operators. are simply deﬁned and have the following properties. We know from our 1 1 study of angular momentum. σj ] = =
h ¯ σi 2 h ¯ σ 2 0 −i i 0 2i ijk σk 1
σz =
1 0 0 −1
They also anticommute. ˆ ˆ Su = u · S The Pauli Spin Matrices. Si S σx = 0 1 1 0 σy
2 σi
≡ = =
[σi . σi . σx σz σx σy = −σy σx {σi . For example lets calculate the basic commutator.11. We will simply represent the h h 1 h + 2 ¯ eigenstate as the upper component of a 2component vector. So the pure eigenstates are. χ+ = χ− = 1 0 0 1
An arbitrary spin one half state can be represented by a spinor.
Both are 1 Bohr e¯ h Magneton.10. but has been measured.10.11. * See Example 17. Traceless matrices of dimension 2.5) which uses a large gradient in the magnetic ﬁeld to exert a force on particles proprtional to the component of spin along the ﬁeld gradient.*
As for orbital angular momentum (L). the eigenstate with the component of spin along the ﬁeld gradient direction either up or down. g = 2 + α + .12: The eigenvectors of Su .10: The eigenvectors of Sx . * See Example 17.10.13: The time development of an arbitrary electron state in a magnetic ﬁeld. Rz (θ) = eiθ/2 0 e
−iθ/2
0
Rx (θ) =
cos θ 2 i sin θ 2
i sin θ 2 cos θ 2
Ry (θ) =
cos θ 2 − sin θ 2
sin θ 2 cos θ 2
Note that the operator for a rotation through 2π radians is minus the identity matrix for any of the axes (because θ appears everywhere).9: The expectation value of Sx .* * See Example 17.7) from the formula Ri (θi ) = eiSi θi /¯ . like the proton or π neutron. we can measure the component of spin along a direction we choose. compared to the formula for orbital angular momenta.. For pointlike particles.259 The σ matrices are the Hermitian.*
The (passive) rotation operators. Any 2 by 2 matrix can be written as a linear combination of the σ matrices and the identity. The surprising result is that the sign of the wave function of all 2 fermions is changed if we rotate through 360 degrees. the magnetic moment due to the spin of an electron is almost exactly equal 2 to the magnetic moment due to the orbital angular momentum in an = 1 state. * See Example 17. A ﬁeld gradient will separate a beam of spin onehalf particles into two beams. + − →
z
. g has been computed in Quantum ElectroDynamics to be a bit over 2.10. Thus. for rotations of the coordinate axes can be computed (see section h 17.14: Nuclear Magnetic Resonance (NMR and MRI)..* * See Example 17. like the electron. μB = 2mc . the gyromagnetic ratio.* * See Example 17.10. g is hard to compute.*
A beam of spin onehalf particles can also be separated by a SternGerlach apparatus (See section 17. For particles with structure. The particles in each of those beams will be in a deﬁnite spin state. We may represent a SternGerlach appartatus which blocks the lower beam by the symbol below.. Because the factor of 2 from g cancels the factor of 2 from s = 1 . eg¯ h σ · B = μB σ · B H = −μ · B = 4mc If we choose the z axis to be in the direction of B. then this reduces to H = μB Bσz .10. eg μspin = − S 2mc This formula has an additional factor of g.11: The eigenvectors of Sy . there is also a magnetic moment associated with internal angular momentum (S). depending on which beam the particle is in.
neither beam is blocked (and we assume we cannot observe which particles go into which beam). For a really unpolarized beam. The appartus below starts with an unpolarized beam. 2
+
+ =
1 0
( 1∗
0∗ ) =
1 0
0 0
We can perform several thought experiments. All of the particles are in the lower beam so nothing is left coming out of the apparatus. the number of particles coming out increased from 0 to N/8. (Note that an unpolarized beam cannot be simply represented by a state vector. So now. The middle part of the apparatus projects the state onto the positive eigenstate of Sx . While the apparatus separates.
1 2 1 2
1 2 1 2
N 2
0 1
=
N 4
. This apparatus does not change the state of the beam! (N particles) → + − →
z
N 2
0 1
→
+ −
→
x
N 2
0 1
→
+ −
→0
z
Now if we block one of the beams separated according to the x direction. The second part of the apparatus blocks the lower separated beam. By blocking one beam. Unpolarized Beam (N particles) → + − →
z
N 2
0 1
→
+ −
→0
z
The result is unaﬀected if we insert an additional apparatus that separates in the x direction in the middle of the apparatus above. This seems a bit strange but the simple explanation is that the upper and lower beams of the middle part of the apparatus were interfering to give zero particles. In such a beam we don’t know the state of any of the particles. half of the particles will go into each of the separated beams.260
¯ This apparatus is equivalent to the operator that projects out the + h eigenstate. the inteference is gone. (N ) → + − →
z
N 2
0 1
→
+ −
→
x
N 4
1 √ 2 1 √ 2
→
+ −
→
z
N 8
1 0
→
Note that we can compute the number of particles coming out of the second (and third) part by squaring the amplitude to go from the input state to the output state N 2 or we can just use the projection operator
1 √ 2 1 √ 2
0 1
1 √ 2
2
=
N 4
1 2 1 2 1 2 1 2
1 √ 2 1 √ 2
1 √ 2
=
1 √ 2 1 √ 2
. With one beam blocked. This state has equal amplitudes to have spin up and spin down along the z direction. particles can get through the whole apparatus. 1/8 of the particles come out of the apparatus.) In the apparatus below. we block the upper beam so that only half of the particles come out of the ﬁrst part of the apparatus and all of those particles are in the deﬁnite state having spin down along the z axis.
E0 − E −A −A E0 − E (E0 − E)2 E − E0 E Now ﬁnd the eigenvectors. This is an example of an SU(2) symmetry. We just have two states which are diﬀerent but completely symmetric. like that in angular momentum (and the weak interactions).9. Substituting auspiciously. There is clearly symmetry between these two states. one with the Nitrogen atom above the plane deﬁned by the three Hydrogen atoms. and the other with the Nitrogen below the plane. The energy eigenvalues can be found from the usual equation. ψabove Hψabove = ψbelow Hψbelow = E0 ψabove Hψbelow = −A H= E0 −A −A E0
We can adjust the phases of the above and below states to make A real.9
17. Feynman starts with two states. chapters 8 and 9) makes a complete study of the two ground states of the Ammonia Molecule. They have identical properties. Feynman’s discussion is very instructive. Since the Nitrogen atom can tunnel from one side of the molecule to the other. Hψ = Eψ a = (E0 ± A) b = (E0 ± A)a (E0 ± A)b = 0 = A2 = ±A = E0 ± A
E0 −A −A E0
a b
E0 a − Ab E0 b − Aa
These are solved if b = ∓a.1
Other Two State Systems*
The Ammonia Molecule (Maser)
The Feynman Lectures (Volume III.261
17. there are cross terms in the Hamiltonian (limiting ourselves to the two symmetric ground states). E0 a ± Aa E0 b ± Ab So the eigenstates are E = E0 − A E = E0 + A
1 √ 2 1 √ 2 1 √ 2 1 − √2
=
(E0 ± A)a (E0 ± A)b
. we get.
We know the eigenvalues of H.
17.. A† = iA† j = ij j + 1δi(j+1)
.. As in the Ammonia molecule. ....10.. A violation of CP symmetry is seen in the decays of these particles. K 0 and K 0 form a very interesting two state system.10. 2 . but the CP (Charge conjugation times Parity) eigenstates are important because they determine how the particles can decay. This makes the diagonal terms of the Hamiltonian slightly diﬀerent.9. there is a small amplitude to make a transition form one to the other.... ⎛1 ⎜0 ⎜ H = hω ⎜ 0 ¯ ⎝ 0 .. 0
3 2
0 0
0 0 0
17..2
The Neutral Kaon System*
¯ The neutral Kaons.
17. . We use the raising operator (See section 9) equation for an energy eigenstate... The basis states are the harmonic oscillator energy eigenstates... . Huj = Ej uj iHj = Ej δij = The Kronecker delta gives us a diagonal matrix..1
Examples
Harmonic Oscillator Hamiltonian Matrix
We wish to ﬁnd the matrix form of the Hamiltonian for a 1D harmonic oscillator. Finally. the Ammonia Maser. The Energy (mass) eigenstates are similar to those in the example above.. √ A† un = n + 1un+1 Now simply compute the matrix element.10
17. Feynman goes on to further split the states by putting the molecules in an electric ﬁeld. .
2
j+
1 2
h ¯ ωδij
⎞ .2
Harmonic Oscillator Raising Operator
We wish to ﬁnd the matrix representing the 1D harmonic oscillator raising operator. ⎟ 2 ⎠ 0 0 7 . Feynman studies the eﬀect of Ammonia in an oscillating Electric ﬁeld.262 The states are split by the interaction term.. ⎟ ⎟ 0 5 . like a magnetic ﬁeld does in the case of spin.
. there is no allowed value of j so the ﬁrst row is all 0.. ⎟ ⎠ .. ⎞ . h ⎛ 0 ⎝1 0 1 0 ψ1 0 1 ⎠ ⎝ ψ2 ⎠ = ψ3 1 0 ⎞⎛ L ψ = aψ ⎞x ⎛
√
⎞ ⎛ ⎞ ψ1 ψ1 2a ⎝ ψ2 ⎠ ≡ b ⎝ ψ2 ⎠ h ¯ ψ3 ψ3
−b 1 0 1 −b 1 = 0 0 1 −b where a =
h ¯ √ b.3
Harmonic Oscillator Lowering Operator
We wish to ﬁnd the matrix representing the 1D harmonic oscillator lowering operator. j=0.... ⎟ ⎟ . ⎟ ⎟ ...... i gives the row and j gives the column. . All he entries will be on a diagonal from that one. Remember that in the Harmonic Oscillator we start counting at 0... This is similar to the last section...4
Eigenvectors of Lx
We will do it as if we don’t already know that the eigenvalues are m¯ .. .. . ....10. . As we have it set up. ⎞ ...
17. . ..263 Now this Kronecker delta puts us one oﬀ the diagonal... 2
−b(b2 − 1) − 1(−b − 0) = 0 b(b2 − 2) = 0
. The lowering operator (See section 9) equation is. Aun = √ nun−1
Now we compute the matrix element from the deﬁnition. jδi(j−1) 0 0 √ 3 0 . Aij = iAj = √ ⎛ 0 1 √ 0 2 0 ⎜0 ⎜ 0 0 A=⎜0 ⎝ 0 0 0 .. 0 0 0 √ 0 0 ⎜ 1 √ ⎜ 2 √ 0 ⎜ 0 † A =⎜ 3 0 ⎜ 0 ⎝ 0 0 0 ....10... so we have an entry for A† in the second row 10 and ﬁrst column. ⎛ 0 0 0 0 √ 4 . . This should be the Hermitian conjugate of A† .
17... For i=0. For i=1...... ⎟ ⎟ . ⎟ ⎠ . 0 0 0 √ 4 ...
we should h go back and ﬁnd the corresponding eigenvector by using the matrix equation. b = + 2. So we would expect that the state with angular momentum +¯ in the x direction. the old x axis becomes the new y (x) axis. You already know what the eigenvalues are.
If we rotate our coordinate system by 90 degrees about the z axis. 0 0 −i Before rotation the state is
(x)
⎛ ψ+¯ = ⎝ h
1 2 1 √ 2 1 2
⎞ ⎠
The rotated state is. For each of these three eigenvalues. These are the eigenvalues we expected for = 1. 2
1∗
1 ∗ √ 2
√
⎝ 1 ⎠ =
1 √ 2
2
c Try calculating the eigenvectors of Ly .5
A 90 degree rotation about the z axis. For example: ψ+¯ ψ+¯ = h h ⎛ 1 ⎞ c2
1 ∗ √ 2
1 2c2 = 1 1 √ . and h a = −¯ .
=
17. h
−1 √ 2
−1 √ 2
⎞
We should normalize these eigenvectors to represent one particle. Lets do the rotation. and b = − 2 or a = 0.264 √ √ There are three solutions to this equation: b = 0.
i 0 ψ = ⎝0 1 0 0
⎛
⎞⎛ 1 ⎞ ⎛ i ⎞ 0 2 2 1 1 0 ⎠ ⎝ √2 ⎠ = ⎝ √2 ⎠ 1 −i −i 2
2
. ψ+ .10. will rotate h (y) into ψ− within a phase factor. ⎞ ⎛ iθ 0 e z 0 Rz (θz ) = ⎝ 0 1 0 ⎠. the solutions are: ⎛ 1 ⎞ ⎛ ψ+¯ = c ⎝ 1 ⎠ h
1 √ 2 √ 2
ψ0¯ h
⎞ 1 = c⎝ 0 ⎠ −1
⎛
ψ−¯ = c ⎝ 1 ⎠ . a = +¯ . ⎛ ⎛ ⎞ ⎞⎛ ⎞ 0 1 0 ψ1 ψ1 ⎝ 1 0 1 ⎠ ⎝ ψ2 ⎠ = b ⎝ ψ2 ⎠ ψ3 ψ3 0 1 0 ⎛ ⎞ ⎛ ⎞ ψ2 ψ1 ⎝ ψ1 + ψ3 ⎠ = b ⎝ ψ2 ⎠ ψ2 ψ3 Up to a normalization constant. 0 0 e−iθz ⎛ ⎞ i 0 0 Rz (θz = 90) = ⎝ 0 1 0 ⎠ .
(y) ψ−
⎛ =⎝
i 2 1 √ 2 −i 2
⎞ ⎠
(x)
This is exactly the same as the rotated state. thus Hψm = μB B ∗ (m¯ ψm ) = (mμB B)ψm h h ¯
Hence the normalized eigenstates must be just those of the operator Lz itself.
17. we get.10. What is ψ− ? We ﬁnd that state by solving the eigenvalue problem. then Lz ψm = m¯ ψm . for the three values of m (eigenvalues of Lz ). h ¯
h Now if ψm is an eigenstate of Lz . ⎛
(y) ψ− = C ⎝ 1 ⎠ −i √ 2 i √ 2
⎞
Normalizing. we get the unnormalized result.265
(y)
Now. h ¯
As usual. i.e.6
Energy Eigenstates of an
= 1 System in a Bﬁeld
Recall that the Hamiltonian for a magnetic moment in an external Bﬁeld is H= μB B Lz . We see that everything in the Hamiltonian above is o a (scalar) constant except the operator Lz . Ly ψ− = −¯ ψ− h ⎛ 0 h ¯ ⎝ √ −1 2i 0
(y) (y)
⎞⎛ ⎞ ⎛ ⎞ 1 0 a a 0 1 ⎠ ⎝ b ⎠ = −¯ ⎝ b ⎠ h −1 0 c c ⎛ √ ⎞ ⎛ ⎞ ib 2 a ⎜ i(c−a) ⎟ ⎝ ⎠ √ = b ⎝ 2 ⎠ −ib c √
2
Setting b = 1. we have
. A 90 degree rotation about the z axis changes ψ+ into (y) ψ− . so that Hψ = μB B Lz ψ = constant ∗ (Lz ψ). what remains is to check whether this state is the one we expect. we ﬁnd the eigenstates (eigenvectors) and eigenvalues of a system by solving the timeindependent Schr¨dinger equation Hψ = Eψ..
now leaving us with a state that we can write. I2 = All the particles in the beam are in the same state. Apparatus 3 blocks that path. and 3? We assume an unpolarized beam coming out of the oven so that 1/3 of the atoms will go into each initial beam in apparatus 1..e.266 ⎛ ⎞ 1 = ⎝0⎠ 0 ⎛ ⎞ 0 = ⎝1⎠ 0 ⎛ ⎞ 0 = ⎝0⎠.7
A series of SternGerlachs
Now that we have the shorthand notation for a SternGerlach apparatus. Em=−1 = −μB B. in fact. we can put some together and think about what happens. This is essentially a classical calculation since we don’t know the exact state of the particles coming from the oven.10. diﬀerent atoms in the beam will have diﬀerent phases. Now apparatus 1 removes the m = 1 component of the beam. the lower one. Apparatus 2 blocks the m = 0 part. I1 = 2 I0 3
We still don’t know the relative phase of those two components and. leaving a state with a mixture of m = 0 and m = −1. 2.
Em=+1 = +μB B
Em=0 = 0
17. ⎧ ⎫ ⎧ ⎫ ⎧ ⎫ ⎨ + ⎬ ⎨+⎬ ⎨ + ⎬ Oven(I0 ) → 0 (I1 ) → 0 (I2 ) → 0 (I3 ) → ⎩ ⎭ ⎩ ⎭ ⎩ ⎭ − z − z − z If the intensity coming out of the oven is I0 . ψ = ψ−
(z)
1 I0 3
The beam in apparatus 3 all goes along the same path. 1
ψm=+1
ψm=0
ψm=−1
and the energy eigenvalues are just the values that E = mμB B takes on for the three values of m i. I3 = 0 The following is a more complex example using a ﬁeld gradients in the z and x directions (assuming the beam is moving in y). what are the intensities at positions 1. The beam will split into only two parts in the second apparatus since there is no m = 1 component left. The following is a simple example in which three successive apparati separate the atomic beam using a ﬁeld gradient along the z direction. ⎧ ⎫ ⎧ ⎫ ⎧ ⎫ ⎨+⎬ ⎨ + ⎬ ⎨ + ⎬ (I1 ) → 0 (I2 ) → 0 (I3 ) → Oven(I0 ) → 0 ⎩ ⎭ ⎩ ⎭ ⎩ ⎭ − z − x − z
.
The probability to get through this apparatus is just the probability to be in the m = 0 beam plus the probability to be in the m = −1 beam. We can compute the intensity of each but lets concentrate on the bottom one because we block the other two. goes into the state ψ− when measured in the x direction (times the intensity coming into the apparatus). ⎛ ⎞ 1 1 (x) (z) 1 ψ− ψ+ = − 1 √2 − 1 ⎝ 0 ⎠ = − 2 2 2 0 So the probability is 1 . Lets compute that probability. After the ﬁrst apparatus. The incoming state is ⎛ 1⎞ −2 1 (x) ⎝√ ⎠ ψ− = 2 1 −2 Remember that the components of this vector are just the amplitudes to be in the diﬀerent m states (using the z axis).267 If the intensity coming out of the oven is I0 . 1 P = −√ 2 I3 =
2
+
1 2
2
=
3 4
3 1 I2 = I0 4 16
Now lets see what happens if we remove the blocking in apparatus 2. the beam splits into 3 parts then recombines yielding (z) the same state as was coming in. ⎧ ⎫ ⎧ ⎫ ⎧ ⎫ ⎨+⎬ ⎨+⎬ ⎨ + ⎬ Oven(I0 ) → 0 (I1 ) → 0 (I2 ) → 0 (I3 ) → ⎩ ⎭ ⎩ ⎭ ⎩ ⎭ − z − x − z Assuming there are no bright lights in apparatus 2. initially in the the state ψ+ . 2. 4 I2 = 1 1 I1 = I0 4 12
(z) (x)
The third apparatus goes back to a separation in z and blocks the m = 1 component. The intensity coming out of apparatus 2 is I2 = I1 . and 3? Now we have a Quantum Mechanics problem. what are the intensities at positions 1. we have an intensity as before I1 = and all the particles are in the state ψ+
(z)
2 I0 3
⎛ ⎞ 1 = ⎝0⎠. The beam separates into 3 parts. ψ+ . 2 (x) (z) I2 = ψ− ψ+ I1 We have written the probability that one particle. 0
The second apparatus is oriented to separate the beam in the x direction. Now with
.
develops with time.8
Time Development of an
= 1 System in a Bﬁeld: Version I
We wish to determine how an angular momentum 1 state develops with time (See Section 6. I3 = 0 By removing the blocking in apparatus 2. what is the state at a later time t? What is the expected value of Lx as h a function of time? We will choose the z axis so that the B ﬁeld is in the z direction. ψ− But we know how each of the energy eigenfunctions develops with time so its easy to write ⎛ ⎞ ⎛ ⎞ h h ψ+ e−iE+ t/¯ ψ+ e−iμB Bt/¯ h ⎠.
. Then we know the energy eigenstates are the eigenstates of Lz and are the basis states for our vector representation of the wave function. in an applied B ﬁeld. ψ(t) = ⎝ ψ0 e−iE0 t/¯ ⎠ = ⎝ ψ0 −iE− t/¯ h h ψ− e ψ− eiμB Bt/¯ h As a concrete example. if an atom is in the state with x component of angular (x) momentum equal to +¯ . ψ+ . ⎛ 1 ⎞ ψ(t = 0) = ψx+ = ⎝ √2 ⎠ ⎛ ψ(t) = ⎜ ψx+ = ⎝
1 2 h e−iμB Bt/¯ 2 1 √ 2 iμB Bt/¯ h e 2 1 √ 2 2 1
⎞ ⎟ ⎠ 0 1 h ¯ √ ⎝1 0 2 0 1
−iμB Bt/¯ h
⎛
ψ(t)Lx ψ(t)
=
h e+iμB Bt/¯ 2
h e−iμB Bt/¯ 2
h ⎞ ⎛ e−iμB Bt/¯ ⎞ 0 2 ⎟ ⎜ 1 √ 1⎠⎝ ⎠ 2 h eiμB Bt/¯ 0
2
ψ(t)Lx ψ(t)
= =
e e 1 h ¯ 1 √ √ +√ 2 2 2 2 2 h ¯ μB Bt μB Bt (4 cos( )) = h cos( ¯ ) 4 h ¯ h ¯
+iμB Bt/¯ h
+
e
iμB Bt/¯ h
2
+
h e−iμB Bt/¯ 1 √ 2 2
Note that this agrees with what we expect at t = 0 and is consistent with the angular momentum precessing about the z axis. let’s assume we start out in the eigenstate of Lx with eigenvalue +¯ . conﬁrming the precession. Assume that we start with a general state which is known at t = 0. In particular. we would see a sine instead of a cosine.268
(z)
the pure state ψ+ going into apparatus 3 and the top beam being blocked there. the intensity dropped from could this happen? What would happen if there were bright lights in apparatus 2?
1 16 I0
to zero. ⎞ ⎛ ψ+ ψ(t = 0) = ⎝ ψ0 ⎠ .4). How
17. no particles come out of apparatus 3.10. If we checked ψLy ψ .
be some arbitrary spin α− Sx = = =
1 2
State
Let χ =
1 2
state. Then the expectation value of the operator
χSx χ ( α∗ + h ∗ ¯ ( α+ 2 α∗ ) − h ¯ 2 0 1 1 0 α− α+ = α+ α− h ∗ ¯ ( α+ α− + α∗ α+ ) .10
Eigenvectors of Sx for Spin
1 2
First the quick solution.269 17. We see that if we are in an eigenstate of Sx the spin measured in the z direction is equally likely to be up and down since the absolute square of either amplitude is 1 . we have 2 0 1 1 0 a b b a
(x)
= = a =
± ± ±b
a b a b
1 √ 2 1 √ 2 1 √ 2 −1 √ 2
χ+
= =
χ−
(x)
These are the eigenvectors of Sx .9 Expectation of Sx in General Spin α+ .10. we know the eigenvalues of Sx ¯ must be ± h . Since there is no diﬀerence between x and z. 2 The remainder of this section goes into more detail on this calculation but is currently notationally challenged. factoring out the constant. in matrix notation. Recall the standard method of ﬁnding eigenvectors and eigenvalues: Aψ = αψ (A − α) ψ = 0 For spin
1 2
system we have. a1 a3 a2 a4 χ1 χ2 =α 1 0 0 1 χ1 χ2
⇒
a1 − α a2 a3 a4 − α
χ1 χ2
=0
.10. − 2
α∗ ) −
17. So.
1 1 . of course). h ¯ 2 0 1 ⇒ 1 0 χ1 χ2 − α 0 0 α χ1 χ2 χ1 χ2 =0 =0
h ¯ 2
0 1
1 . for the operator A = Sx = in matrix notation. or α2 − h ¯2 =0 4 ⇒ α=± h ¯ 2
These are the two eigenvalues (we knew this. we ﬁnd for the eigenvalue α = −¯ /2. This gives the “characteristic equation” which for spin 1 systems will be a quadratic equation in the eigenvalue α: 2 a1 − α a3 a2 = (a1 − α)(a4 − α) − a2 a3 = 0 a4 − α
α2 − (a1 + a4 )α + (a1 a4 − a2 a3 ) = 0 whose solution is α± = (a1 + a4 ) ± 4 (a1 + a4 ) − (a1 a4 − a2 a3 ) 2
2
To ﬁnd the eigenvectors. we obtain −α+ h ¯ /2 h ¯ /2 −α+ χ1 χ2 = −¯ /2 ¯ /2 h h h ¯ /2 −¯ /2 h χ1 χ2 = h ¯ 2 −1 1 1 −1 χ1 χ2 =0
The last equality is satisﬁed only if χ1 = χ2 (just write out the two component equations to see this). the determinant of the matrix must be zero. 0
−α ¯ /2 h h ¯ /2 −α
The characteristic equation is detSx − α = 0.270 For a matrix times a nonzero vector to give zero. h 1 (x) χ− = √ 2 1 −1 . Now speciﬁcally. the eigenvalue equation (Sx −α)χ = 0 becomes. Now. we simply replace (one at a time) each of the eigenvalues above into the equation a1 − α a2 χ1 =0 a3 a4 − α χ2 and solve for χ1 and χ2 .
. substituting α+ back into the eigenvalue equation. Hence the normalized eigenvector corresponding to the eigenvalue α = +¯ /2 is h 1 (x) χ+ = √ 2 Similarly.
10.11 Eigenvectors of Sy for Spin
1 2
To ﬁnd the eigenvectors of the operator Sy we follow precisely the same procedure as we did for Sx (see previous example for details). Hence the two eigenvalues and their corresponding normalized eigenvectors are α+ = +¯ /2 h 1 (y) χ+ = √ 2 1 (y) χ− = √ 2 1 i 1 −i
h α− = −¯ /2
17. lets take the u direction to be in the xz plane. or α2 − h ¯2 =0 4 ⇒ α=± h ¯ 2
These are the same eigenvalues we found for Sx (no surprise!) Plugging α+ back into the equation.10. sin(30)) = ( ˆ ˆ calculate the matrix Su = u · S.
We may simply
1 2 3 4
3 4
−1 2
. we obtain h ¯ −1 −i −α+ −i¯ /2 χ1 h χ1 = =0 i¯ /2 −α+ h χ2 χ2 i −1 2 Writing this out in components gives the pair of equations −χ1 − iχ2 = 0 and iχ1 − χ2 = 0 which are both equivalent to χ2 = iχ1 . The steps are: 1. 0. 30 degrees from the x axis.12
Eigenvectors of Su
As an example. Substitute the eigenvalues back into the original equation 4.271 17. in matrix notation the eigenvalue equation 0 χ1 χ2 =0
−α −i¯ /2 h i¯ /2 h −α
The characteristic equation is detSy − α = 0. 2 ). Solve the characteristic equation for the eigenvalues α± 3. Write the eigenvalue equation (Sy − α)χ = 0 2. between the positive x and z axes. 0. Solve this equation for the eigenvectors Here we go! The operator Sy = becomes
h ¯ 2
0 i
−i . we ﬁnd that χ2 = −iχ1 . so that. The unit vector is then u = (cos(30). Su = ⎛ 3 1 h ¯⎝ Sx + Sz = 4 2 2 ⎞ ⎠
3 1 4 . Repeating the process for α− .
we see that a rotation of 60 degrees moves the u axis to the old z axis. we have a = −
1 3 b. and the lower component (b) is the amplitude to have spin down. By using the rotation operator. We know that the energy eigenstates evolve with time quite simply (recall the h separation of the Schr¨dinger equation where T (t) = e−iEt/¯ ). We must think carefully about exacty what rotation to do. 2
Factoring out the
h ¯ 2.13
Time Development of a Spin
1 2
State in a B ﬁeld
a and we have chosen the z axis to be in b the ﬁeld direction. For the negative
giving the eigenvector χ− =
−1 2
3 4
. The upper component of the vector (a) is the amplitude to have spin up along the z direction. giving the eigenvector χ+ =
(u)
3 4 1 2
.
the equation for the eigenvectors is. ⎛ ⎝
1 2 3 4 3 4
⎞ ⎠ a b
3 4b ⎠ 1 2b
⎛ ⎝
1 −2 1 2a
=± ⎞ =±
a b a b
+ −
3 4a
For the positive eigenvalue. the phase of the eigenvectors is consistent (z) with the choice made for χ± .10. the spin up and spin down states are also the energy eigenstates with energy eigenvalues of μB B and −μB B respectively. Thinking about the signs carefully. Ry = Ry (−60) = cos θ 2 − sin θ ⎛ 2 sin θ 2 cos θ 2
1 −2 3 4 3 4 1 2 1 −2 3 4 (z)
cos(30) − sin(30) =⎝ sin(30) cos(30) 1 2 ⎞ ⎛ 3 1 −2 4 (u) ⎠ 1 = χ+ = ⎝ 0 1 3 2 4 ⎞ ⎛ 3 1 −2 4 (u) ⎠ 0 = χ− = ⎝ 1 1 3
2 4
3 4
⎞ ⎠
This gives the same answer. For most problems.272
¯ We expect the eigenvalues to be ± h as for all axes. we have a = eigenvalue. this is not important but it is for some. We take the states χ± and rotate the axes so that the u axis is where the z axis was. Clearly we need a rotation about the y axis. So its simple to write down the time o Assume that we are in an arbitrary spin state χ(t = 0) =
.
√ (u) 3b. Because of our choice of axes.
17. There is an alternate way to solve the problem using rotation matrices. Of course each of these could
be multiplied by an arbitrary phase factor.
10.273 evolved state vector.14
Nuclear Magnetic Resonance (NMR and MRI)
Nuclear Magnetic Resonance is an important tool in chemical analysis. most of the protons fall into the lower of the two states.
h ae−iμB Bt/¯ h beiμB Bt/¯
χ(t) =
=
ae−iωt beiωt
where ω =
μB B h . Surprisingly. We then have
χ(t) χ(t)Sx χ(t)
= = = = h ¯ 2
1 √ e−iωt 2 1 √ eiωt 2 1 √ e+iωt 2
. a strong static B ﬁeld is applied. We now use an electromagnetic wave (RF pulse) to excite some of the protons back into the higher energy state. Because g = 2 the rate is twice as high as for = 1.
. A spin 1 proton in a hydrogen nucleus then has two 2 energy eigenstates. After some time. In basic NMR. Magnetic Resonance Imaging uses the same principle to get an image (of the inside of the body for example). The proton’s magnetic moment interacts with the oscillating B ﬁeld of the EM wave. ¯
So let’s say we start out in the state with spin up along the x axis. it uses the spin magnetic moments of nuclei (particularly hydrogen) and resonant excitation.
17. we can calculate this process already. χ(0) =
1 √ 2 1 √ 2
.
1 √ e−iωt 2
h ¯ 2
0 1
1 0
1 √ e−iωt 2 1 √ eiωt 2
1 √ e+iωt 2
1 √ e−iωt 2
1 √ e+iωt 2 1 √ e−iωt 2
h ¯ h ¯ 1 +2iωt e + e−2iωt = cos(2μB Bt/¯ ) h 22 2
So again the spin precesses around the magnetic ﬁeld. As the name implies.
The ﬁrst term will only cause signiﬁcant transitions if ω ≈ 2ω0 . Note that this is exactly the condition that requires the energy of the photons in the EM ﬁeld E = hω to be equal to the energy diﬀerence between the two ¯ spin states ΔE = 2¯ ω0 . The magnetic moment is 2.11. The second term oscillates very rapidly. Let’s choose our strong static B ﬁeld to be in the z direction and the polarization on our oscillating EM wave so that the B ﬁeld points in the x direction.274
m=1/2 Ε=μΒ
Pulse of oscillating B field excites spin state if hν=2μΒ
As excited state decays back to ground state. the Hamiltonian is H = −μ · B = gp e¯ gp h gp e σ · B = μN σ · B S ·B = 2mp c 4mp c 2
Note that the gyromagnetic ratio of the proton is about +5. The conservation of energy condition must be satisﬁed well enough to get a h
. EM radiation is emittted
m=+1/2
Ε=−μΒ
As we derived. gp gp Bz Bx cos ωt H = μN (Bz σz + Bx cos(ωt)σx ) = μN Bx cos ωt −Bz 2 2 Now we apply the time dependent Schr¨dinger equation. Diﬀerent nuclei will have diﬀerent gyromagnetic ratios. The EM wave has (angular) frequency ω.8) of these equations represents and early example of time dependent perturbation theory.79 μN (Nuclear Magnetons). giving us more tools to work with. −iω1 i(ω−2ω0 )t d (be−iω0 t ) = (e + e−i(ω+2ω0 t) ) dt 2 Terms that oscillate rapidly will average to zero.6. o i¯ h i¯ h dχ dt a ˙ ˙ b a ˙ ˙ b = = = = Hχ gp Bz a Bx cos ωt μN b Bx cos ωt −Bz 2 gp μN a Bx cos ωt Bz −i −Bz b Bx cos ωt 2¯ h −i ω0 ω1 cos ωt ω1 cos ωt −ω0 a b
The solution (see section 17.
But we already see that the h energy terms e−iEt/¯ of standard wave mechanics will require energy conservation with photon energies of E = hω. ¯ NMR is a powerful tool in chemical analysis because the molecular ﬁeld adds to the external B ﬁeld so that the resonant frequency depends on the molecule as well as the nucleus. All the ﬁeld variation takes some time though.1
Derivations and Computations
The = 1 Angular Momentum Operators*
We will use states of deﬁnite Lz . Ultimately.11. we can get to 3D. These emit EM radiation at the same frequency and we can detect it after the stronger input pulse ends (or by more complex methods). This allows us to cause transitions to the higher energy state. We don’t yet know why the higher energy state will spontaneously decay to the lower energy state. We can put a gradient in Bz so that only a thin slice of the material has ω tuned to the resonant frequency. If we vary B as a function of time during the decay. we typically concentrate on one nucleus like hydrogen. the Y1m . we will have to quantize the ﬁeld. In MRI. a very powerful tool for scanning materials (a la Star Trek) is possible. In NMR.275 signiﬁcant transition rate. We can learn about molecular ﬁelds or just use NMR to see what molecules are present in a sample. Therefore we can excite transitions to the higher energy state in only a slice of the sample. MRIs are a very safe way to examine the inside of the body. we observe the transitions back to the lower energy state. we now understand the basis of the technique. Actually we will ﬁnd later that for rapid transitions. To calculate this. While there are more complex methods used in MRI.11
17. So we have proven our personhood and can calculate that we should set the frequency ω of our EM wave according to the energy diﬀerence between the two spin states. energy conservation does not have to be exact. If we vary (in the orthogonal direction!) the B ﬁeld during the decay of the excited state. we can get a two dimensional picture. m Lz  m = m¯ δm m h ⎛ ⎞ 1 0 0 Lz = h ⎝ 0 0 0 ⎠ ¯ 0 0 −1
m L±  m L+
= =
L−
=
( + 1) − m(m ± 1)¯ δm (m±1) h √ ⎛ ⎞ 2 √ 0 0 h⎝0 0 ¯ 2⎠ 0 0 0 ⎞ ⎛ 0 0 0 √ h⎝ 2 √ 0⎠ ¯ 0 2 0 0 ⎞ 1 0 0 1⎠ 1 0
Lx
=
⎛ 0 1 h ¯ ⎝ (L+ + L− ) = √ 1 2 2 0
.
17.
Just do it. we get the transformed coordinates x y We can Taylor expand any function f . Let θz = ndφ. ∂x ∂y h ¯ = = x − dφy y + dφx. Then i θz h Lz )n = eiθz Lz /¯ . y ) = f (x. We can verify it by using the 1 log of the quantity.11.
. we get the identity. y) − ∂f i ∂f dφy + dφx = (1 + dφLz )f (x.11. Ly ] = 1 0 2i 0 1 ⎛⎛ ⎞ ⎛ −1 0 1 1 h ¯ 2 ⎝⎝ 0 0 0⎠−⎝ 0 2i −1 0 1 −1
The other relations will prove to be correct too. Derive the matrix operators for = 2. as they must.3
Derive the Expression for Rotation Operator Rz *
The laws of physics do not depend on what axes we choose for our coordinate system.
17.There is rotational symmetry. y). f (x .2
Compute [Lx .276 ⎞ 0 1 0 1 h ¯ (L+ − L− ) = √ ⎝ −1 0 1 ⎠ 2i 2i 0 −1 0 ⎛
Ly
=
What is the dimension of the matrices for = 2? Dimension 5.
17. Its a reassuring check and a calculational example.
n→∞
lim ln(1 +
i θz i θz i Lz )n = n( L z ) = θz L z h ¯ n h ¯ n h ¯
So exponentiating. If we make an inﬁnitesimal rotation (through and angle dφ) about the zaxis. First we expand ln(x) about x = 1: ln(x) = ln(1) + x x=1 (x − 1) = (x − 1).
So the rotation operator for the function is Rz (dφ) = (1 + i dφLz ) h ¯
A ﬁnite rotation can be made by applying the operator for an inﬁnitesimal rotation over and over. converting the limit to an exponential is a known identity. Ly ] Using Matrices * ⎞⎛ 0 0 1 1 ⎠ ⎝ −1 0 0 0 −1 ⎞⎞ 0 1 h ¯2 0 0 ⎠⎠ = 2i 0 −1 ⎞ ⎛ ⎞⎛ ⎞⎞ 0 0 1 0 0 1 0 1 ⎠ − ⎝ −1 0 1 ⎠ ⎝ 1 0 1 ⎠⎠ 0 0 −1 0 0 1 0 ⎛ ⎞ ⎛ ⎞ −2 0 0 1 0 0 ⎝ 0 0 0 ⎠ = i¯ ¯ ⎝ 0 0 0 ⎠ = i¯ Lz hh h 0 0 2 0 0 −1
⎛⎛ 0 1 h ¯ 2 ⎝⎝ [Lx . Rz (θz ) = lim (1 + n→∞ h ¯ n The last step.
We h now must look at the sums for each term in the matrix and identify the function it represents. The ¯ s all cancel out. Lz h ¯
0
⎛
All the odd powers are the same. There is only n! one contribution to the middle term. We get (−iθ) term n.5
Compute the
= 1 Rotation Operator Ry (θy ) *
∞ h eiθLy /¯ = n=0 iθLy h ¯ n
n!
⎞ 1 0 0 Ly = ⎝0 1 0⎠ h ¯ 0 0 1 ⎛ ⎞ 1 0 1 0 Ly 1 ⎝ −1 0 1 ⎠ =√ h ¯ 2i 0 −1 0 ⎛ ⎞ 1 0 −1 2 Ly 1⎝ 0 2 0 ⎠ = h ¯ 2 −1 0 1
0
⎛
.4 Compute the = 1 Rotation Operator Rz (θz ) *
∞ h eiθLz /¯ = n=0 iθLz n h ¯
n! ⎞ 0 0 1 0⎠ 0 1 ⎞ 0 0 0 0 ⎠ 0 −1 ⎞ 0 0 0 0⎠ 0 1 ⎞ 0 h 0 ⎠ = Lz /¯ −1
1 = ⎝0 0 ⎛ 1 1 Lz = ⎝0 h ¯ 0 ⎛ 2 1 Lz = ⎝0 h ¯ 0 ⎛ 3 1 0 Lz = ⎝0 0 h ¯ 0 0 . −iθz 0 0 e
17.11. All the nonzero even powers are the same. we get a 1 times (iθ) . This is just e−iθ . If we look n at the sum for the upper left term of the matrix. The rest of the n! terms are zero.277 17.. This is just eiθ . ⎞ ⎛ iθ 0 e z 0 Rz (θz ) = ⎝ 0 1 0 ⎠. The lower right term is like the upper n left except the odd terms have a minus sign. that is a one from n = 0.11..
⎛ ⎛ ⎞ ⎞ ⎛ ⎞ 1 0 −1 0 0 1 0 1 1 0 ⎠ + sin(θ) √ ⎝ −1 0 1 ⎠ + (cos(θ) − 1) ⎝ 0 2 0 ⎠ 2 2 −1 0 1 1 0 −1 0
h eiθLy /¯
1 = ⎝0 0
0 1 0
Putting this all together. 2 1 (1 + cos(θy )) 2
17. we get ⎛1 ⎜ Ry (θy ) = ⎝
2 (1 + 1 − √2 1 2 (1 −
1 √ sin(θy ) cos(θy )) 2 sin(θy ) cos(θy ) 1 cos(θy )) − √2 sin(θy )
⎞ 1 2 (1 − cos(θy )) ⎟ 1 √ sin(θy ) ⎠. We h now must look at the sums for each term in the matrix and identify the function it represents..278 ⎞ 0 2 0 1 1⎝ = √ −2 0 2 ⎠ = 2i 2 0 −2 0 . The n = 0 2 term is is missing so subtract 1. . χ+ χ− S z χ± Sz = = = = 1 0 0 1 h ¯ ± χ± 2 h ¯ 1 0 2 0 −1
Its easy to see that this is the only matrix that works. .. • The n = 1. as the basis states.
• The n = 2. Now we do the raising and lowering operators. terms sum to sin(θ)
iLy h ¯
. It must be diagonal since the basis states are eigenvectors of the matrix. 6.. 4. 3. The middle matrix element is twice the other even terms.. 5..11. • The n = 0 term contributes 1 on the diagonals. terms (with a 1 in the matrix) are nearly the series for 1 cos(θ).6
Derive Spin
1 2
Operators
We will again use eigenstates of Sz . S + χ+ S + χ− = = 0 s(s + 1) − m(m + 1)¯ χ+ = hχ+ h ¯
. The correct eigenvalues appear on the diagonal. The ¯ s all cancel out. ⎛
Ly h ¯
3
Ly h ¯
All the odd powers are the same.. All the nonzero even powers are the same.
h ¯ 2 h ¯ 2 0 1 1 0 0 −i i 0
17.
σz σy σx
= = =
1 0 0 −1 0 −i i 0 0 1 1 0
2 σz = 2 σy = 2 σx =
1 0 1 0 1 0 0 1
0 1 0 1
Doing the sums ⎛ Rz (θ) =
∞
θ ⎜ ei 2 σz = ⎝ n=0
( iθ )n 2
n! ∞
0 (
−iθ 2
⎞ ⎟ = ) ⎠
n
0 ⎛ Ry (θ) = ⎜ ⎜ ⎝
∞ n=0.4... Traceless matrices. ∞ n=0
ei 2 0
θ
0 θ e−i 2
n! ∞
( )
iθ 2
n
n!
−i
n
( iθ )n 2
n!
n
⎞ ⎟ ⎟= ⎠ cos θ 2 − sin θ 2 sin θ 2 cos θ 2
i
n=1.2...279 0 1 0 0 s(s + 1) − m(m − 1)¯ χ− = hχ− h ¯ h ¯ 0 0 1 0
S+ S − χ− S − χ+ S−
= = = =
h ¯ 0
We can now calculate Sx and Sy .5.. we derived the expression for the rotation operator for orbital angular momentum vectors.11.5.7
Derive Spin
1 2
Rotation Matrices *
In section 17. 1 (S+ + S− ) = 2 1 Sy = (S+ − S− ) = 2i Sx = These are again Hermitian.. The rotation operators for internal angular momentum will follow the same formula.2..11.3.4.
(2)
n!
. ∞ iθ n=0.. Rz (θ) Rx (θ) Ry (θ) ei 2 σj
θ
= = = =
e
iθSz h ¯ θ θ
= ei 2 σz
θ
ei 2 σx ei 2 σy
∞ n=0 iθ n 2
n!
n σj
n We now can compute the series by looking at the behavior of σj .3.
( iθ ) 2
n!
n=1.3.
when the EM wave starts.. Note that this is exactly the condition that requires the energy of the photons in the EM ﬁeld E = hω to be equal to the energy diﬀerence between the two spin states ΔE = 2¯ ω0 . a = 1 and b = 0.3. we need to keep adding b in phase with b.
( iθ )n 2
n!
iθ 2 n
⎞ cos θ 2 i sin θ 2 i sin θ 2 cos θ 2
⎟ ⎟= ( ) ⎠
n!
Note that all of these rotation matrices become the identity matrix for rotations through 720 degrees and are minus the identity for rotations through 360 degrees.8
NMR Transition Rate in a Oscillating B Field
We have the time dependent Schr¨dinger equation for a proton in a static ﬁeld in the z direction plus an o oscillating ﬁeld in the x direction..11.2. Then we have a = ˙ a = ˙ b = ˙ b = −iω0 a 1e−iω0 t −iω1 cos ωta + iω0 b = −iω1 cos ωte−iω0 t + iω0 b −iω1 i(ω−ω0 )t (e + e−i(ω+ω0 )t ) + iω0 b 2
Now comes the one tricky part of the calculation. This could be hard but we will do it only near t = 0. To get b to grow.. The diagonal terms in the Hamiltonian cause a very ˙ rapid time dependence to the amplitudes.. d (be−iω0 t ) = dt = −iω1 i(ω−2ω0 )t + e−i(ω+2ω0 )t ) + iω0 be−iω0 t − iω0 be−iω0 t (e 2 −iω1 i(ω−2ω0 )t (e + e−i(ω+2ω0 )t ) 2
Terms that oscillate rapidly will average to zero.4.
17. To get a net change in be−iω0 t . Now we have to solve this o system of two equations. let’s compute the time derivative of be .3. that is.5... ¯ h −iω1 2 −iω1 t 2
d (be−iω0 t ) = dt be−iω0 t =
. Then the ﬁrst term is important and we can neglect the second which oscillates with a frequency of the order of 1011 . n! ⎜ n ∞ ⎝ ( iθ ) 2
n=1. i¯ h i¯ h dχ dt a ˙ ˙ b a ˙ ˙ b = Hχ = gp Bz a Bx cos ωt μN −Bz b Bx cos ωt 2 gp μN a Bx cos ωt Bz = −i b Bx cos ωt −Bz 2¯ h
= −i
ω0 ω1 cos ωt ω1 cos ωt −ω0
a b
So far all we have done is plugged things into the Schr¨dinger equation. −iω0 t To see that clearly. n!
( iθ )n 2
∞ n=1. Assume that at t = 0.2.280 ⎛ Rx (θ) =
∞
⎜ n=0. the nucleus is in the lower energy state..5. ∞ n=0.4. we need to have ω ≈ 2ω0 ..
and the system is found to be in the eigenstate ¯ with the larger eigenvalue. the magnetic ﬁeld is very quickly switched to the x direction. What is the probability ¯ that the value − h will be found? 2
3.
8. we can only cause transitions if the EM ﬁeld is tuned so that ω ≈ 2ω0 which means the photons in the EM wave have an energy equal to the diﬀerence in energy between the spin down state and the spin up state. Calculate the as a basis.) 5. An electron is in an eigenstate of Sx with eigenvalue h . Find the eigenstates of the harmonic oscillator lowering operator A.
17. a measurement of the y component of the spin is made. Actually. = 1 operator for arbitrary rotations about the xaxis. What are the eigenstates and eigenvalues of the operator Sx + Sy ? 2 Suppose a measurement of this quantity is made. where the uaxis is assumed to be 2 2 2 2 in the x − y plane rotated by and angle θ from the xaxis.12
Homework Problems
⎛ ⎞ 1 1. we will see that the probability increases linearly with time and there is a delta function of energy conservation. The transition rate increases as we increase the strength of the oscillating B ﬁeld. Consider a system of spin 1 . Find the relative intensities of the three beams separated in the second apparatus. Make sure that the states α are normalized so that αα = 1. Sy = + h . once we do the calculation (only a bit) more carefully. A second apparatus separates the beam according to its angular momentum component along the uaxis. After another time interval T . What is the probability that a subsequent measurement of Sy yields h ? 2 4.281 It appears that the amplitude grows linearly with time and hence the probability would grow like t2 . Particles with angular momentum 1 are passed through a SternGerlach apparatus which separates them according to the zcomponent of their angular momentum. b) Sz = − h . Compute α α . What is the probability that a 26 4 measurement of Lx yields a value of 0?
¯ 2. The Hamiltonian matrix is given to be ⎞ 8 4 6 H = hω ⎝ 4 10 4 ⎠ . At that time it is 2 2 placed in a constant magnetic ﬁeld B in the z direction. At that instant. Only the m = −1 component is allowed to pass through the apparatus. Suppose α is another such state with a diﬀerent eigenvalue. What are the amplitudes to ﬁnd the 2 ¯ ¯ ¯ ¯ electron with a) Sz = + h . In any case. The spin is allowed to precess for a time T . An angular momentum 1 system is in the state χ = √1 ⎝ 3 ⎠. Use the usual Lz eigenstates ⎛
¯ 7. Su = + h . Do this by ﬁnding the coeﬃcients nα where n is the nth energy eigenstate. Would you expect these states to be orthogonal?
. What are the eigenfunctions and eigenvalues of the operator Lx Ly + Ly Lx for a spin 1 system? 6. We will do this more generally in the section on time dependent perturbation theory. ¯ 6 4 8 What are the eigenenergies and corresponding eigenstates of the system? (This isn’t too messy. A spin 1 particle is in an eigenstate of Sy with eigenvalue + h at time t = 0. 9. The uaxis and the zaxis are both perpendicular to the beam direction but have an angle θ between them. They should satisfy the equation Aα = αα .
ψ2 Hψ2 = ψ3 Hψ3 = E2 . Write out the upper left 5 × 5 part of the matrix. 1 h Find the time development (matrix) operator e−iHt/¯ in the usual basis.13
Sample Test Problems
1. particle is in a magnetic ﬁeld in the x direction giving a Hamiltonian H = μB Bσx . What is the 7. What is the −i probability that a measurement of the x component of spin yields zero? What is the probability that a measurement of the y component of spin yields +¯ ? h 4. If χ(t = 0) = . and ψ2 Hψ3 = α. ⎛ √ ⎞ 2 1 3. ψ1 Hψ3 = 0. What are the energy eigenvalues and eigenstates of the system? At t = 0 the system is in the state ψ2 . √ 3 1 1 √ . the matrix elements are given as ψ1 Hψ1 = E1 . What is ψ(t)? 5. what intensity comes out? I→ I→ I→ I→ I→ + − + − + − + − + − →
z
→
z
+ − + − →
u
→?
x
→
z
→?
u
+ − + − + −
+ − + − + −
→?
z
→
z
→
u
→?
z
→
z
→
u
→?
x
17. * We have shown that the Hermitian conjugate of a rotation operator R(θ) is R(−θ). Let’s deﬁne the u axis to be in the xz plane. 11. then the set φi = R(θ)φi are also orthonormal and complete. Given an unpolarized spin 1 beam of intensity I going into the following 2 SternGerlach apparati. ψ1 Hψ2 = 0. 2. b) Write the upper left 5 by 5 part of the p2 matrix. A spin 2 system is in the following state in the usual Sz basis: χ = 5 1+i 1 probability that a measurement of the x component of spin yields + 2 ? 6. In a three state system. Find the (normalized) eigenvectors and eigenvalues of the Sx (matrix) operator for s = 1 in the usual (Sz ) basis. Given that un is the nth one dimensional harmonic oscillator energy eigenstate: a) Evaluate the matrix element um p2 un . Use this to prove that if the φi form an orthonormal complete set. Find the matrix which represents the p2 operator for a 1D harmonic oscillator. ﬁnd 0 χ(t). between the positive x and z axes and at an angle of 30 degrees to the x axis. * A spin
1 2
. A spin 1 system is in the following state in the usual Lz basis: χ = √5 ⎝ 1 + i ⎠. Assume all of the matrix elements are real.282 10.
(in the usual Lz eigenstate basis): ⎛ ⎞ i 1 ⎝ √ ⎠ χ= √ 2 . 2
15. 2
13. The particle is in a magnetic 2 2 ﬁeld B = (0. 0. 0. A spin 1 object is in an eigenstate of Sz with eigenvalue h at t=0. A spin
1 2
system is in the state χ =
1 √ 5
(in the usual Sz eigenstate basis). The particle is in a magnetic 2 2 ﬁeld B = (0.
¯ 16. A spin 1 object is in an eigenstate of Sy with eigenvalue h at t=0. Find the probability to measure Sy = + h as a 2 function of time. What is the What is the probability that a measurement of
probability that a measurement of Sx yields h Sy yields −¯ ? 2
−¯ h 2 ?
¯ 9. B. A spin 1 system is in the following state. 0) which makes the Hamiltonian for the system H = μB Bσy . Find the ¯ spin state of the particle as a function of time. The particle is in a magnetic 2 2 ﬁeld B = (0. Find the probability ¯ to measure Sy = h as a function of time. Find the probability ¯ to measure Sy = h as a function of time. What are the eigenvectors and eigenvalues for the spin
1 2
operator Sx + Sz ?
¯ 12. 5 1+i What is the probability that a measurement of Lx yields 0? What is the probability that a measurement of Ly yields −¯ ? h
¯ 14. Two degenerate eigenfunctions of the Hamiltonian are properly normalized and have the following properties.283 i 2
8. B) which makes the Hamiltonian for the system H = μB Bσz .
. A (spin 1 ) electron is in an eigenstate of Sy with eigenvalue − h at t = 0. 2
10. The particle is in a 2 2 magnetic ﬁeld B = (0. A spin 1 object is in an eigenstate of Sy with eigenvalue h at t=0. 0. Hψ1 = E0 ψ1 P ψ1 = −ψ2 Hψ2 = E0 ψ2 P ψ2 = −ψ1
What are the properly normalized states that are eigenfunctions of H and P? What are their energies? 11. A spin 1 particle is placed in an external ﬁeld in the u direction such that the Hamiltonian is given by √ 1 3 H=α Sx + Sy 2 2 Find the energy eigenstates and eigenvalues. Find the probability ¯ to measure Sz = h as a function of time. B) which makes the Hamiltonian for the system H = μB Bσz . B) which makes the Hamiltonian for the system H = μB Bσz .
. It is measured that the maximum electron energy is 2.1 eV for 2000 Angstrom light and 0. A 200 keV photon collides with an electron initially at rest. 2 8. Use the energy density in a cavity as a function of frequency and T u(ν. 7. 2. The photon is observed to scatter at 90 degrees in the electron rest frame.
−∞
f (x)δ(x−x0 ) dx = f (x0 ) Find the momentum
6.3 ± 0. 4. Determine Planck’s constant and its error based on these measurements. Use the calculation of a spreading Gaussian wave packet to ﬁnd the fractional change in size of a wave packet between t = 0 and t = 1 second for an electron localized to 1 Angstrom.04 eV for 2580 Angstrom light. • a 1 eV electron • a 104 MeV proton • a 1 gram lead ball moving with a velocity of 100 cm/sec. Estimate the kinetic energy of a neutron conﬁned inside the same nucleus. Use the uncertainty principle to estimate the energy of the ground state of a harmonic oscillator p2 with the Hamiltonian H = 2m + 1 kx2 . Now ﬁnd the fraction change for a 1 gram weight localized to 1 nanometer. The Dirac delta function has the property that space wave function φ(p) if ψ(x) = δ(x − x0 ).284
18
18.90 ± 0. What are the kinetic energies of the electron and photon after the scattering? 3. Estimate the kinetic energy of an electron conﬁned to be inside a nucleus of radius 5 Fermis. T ) = ν3 8πh c3 ehν/kT − 1
to calculate the emissive power of a black body E(λ. What is the DeBroglie wavelength for each of the following particles? The energies given are the kinetic energies.
∞
5.1
Homework Problems 130A
HOMEWORK 1
1. T ) as a function of wavelength and temperature. A polished Aluminum plate is hit by beams of photons of known energy.
Directly calculate the the RMS uncertainty in x for the state ψ(x) = Δx = ψ(x − x )2 ψ . i 6.
. Is energy conserved?
2 8.
Remember that the wave functions go to zero at inﬁnity. 4. Consider the functions of one angle ψ(θ) with −π ≤ θ ≤ π and ψ(−π) = ψ(π). 0) = a for 2 − a < x < 0 and the ψ(x. Calculate the commutator [p2 . Suddenly the walls of the box are completely removed.285
18. The wave function for a particle is initially ψ(x) = Aeikx + Be−ikx . A particle is in the ﬁrst excited state of a box of length L. Show that the ¯ d angular momentum operator L = h dθ has real expectation values. A particle is in a box with solid walls at x = ± a . What is that state? Now one wall of the box is suddenly moved outward so that the new box has length D. Prove that the parity operator deﬁned by P ψ(x) = ψ(−x) is a hermitian operator and ﬁnd its possible eigenvalues. 2.
a π
1 4
e
−ax2 2
by computing
3. Write the state at t = 0 as φ(p). Would it be correct (and why) to use φ(p) to compute ψ(x. Show that
ψ ∗ (x)xψ(x)dx =
−∞ −∞
φ∗ (p) i¯ h
∂ ∂p
φ(p)dp. 2(A − B) 2(A + B)
7. What is the probability for the particle to be in the ground state of the new box? What is the probability for the particle to be in the ﬁrst excited state of the new box? You may ﬁnd it useful to know that sin(Ax) sin(Bx)dx = sin ((A − B)x) sin ((A + B)x) − . Write ψ(x. t)?
9.2
Homework 2
∞ ∞
1. 0) = 0 everywhere else. t) in terms of the energy eigenstates. Use this to calculate Δp in a similar way to the Δx calculation. Calculate pn for the state in the previous problem. Calculate the probability to ﬁnd that the particle has momentum between p and p + dp. x2 ]. What is the probability ﬂux j(x)? 10. A particle is initially in the nth eigenstate of a box of length L. The state at t = 0 is constant ψ(x. Write this state as a sum of energy eigenstates 2 of the particle in a box. 5.
. 2.3 × 10−13 cm. Assume that the wavefunction is x < −a Aeikx + Be−ikx ψ(x) = x>a Ceikx + De−ikx Relating the “outgoing” waves to the “incoming” waves by the matrix equation C B show that S11 2 + S21 2 = 1 S12 2 + S22 2 = 1
∗ ∗ S11 S12 + S21 S22 = 0
=
S11 S21
S12 S22
A D
Use this to show that the S matrix is unitary. A general one dimensional scattering problem could be characterized by an (arbitrary) potential V (x) which is localized by the requirement that V (x) = 0 for x > a.) 4. Find the depth of the potential in MeV. (The equation to solve is transcendental.286
18. Assume the range of the potential is 2. Calculate the S matrix for the potential V (x) = V0 0 x < a x > a
and show that the above conditions are satisﬁed. 5. Find the three lowest energy wavefunctions for the harmonic oscillator. the binding energy is 2.3
Homework 3
1. 3.9 MeV. Assume the potential for particle bound inside a nucleus is given by V (x) = −V0 h2 ( +1) ¯ 2mx2 x<R x>R
and that the particle has mass m and energy e > 0. and the mass of the particle is 940 MeV. Estimate the lifetime of the particle inside this potential. The odd bound state solution to the potential well problem bears many similarities to the zero angular momentum solution to the 3D spherical potential well.
In a 1D square well. Prove the Schwartz inequality  ψφ  ≤ ψψ φφ . there is always at least one bound state. a) Find the solution to the Schr¨dinger equation for this problem. c) Calculate the probability for a particle in the beam to be reﬂected by the potential and the probability to be transmitted. How can there be a bound state even for small values of V0 ?
1 3. 2. 5. The hyperparity operator H has the property that H 4 ψ = ψ for any state ψ. Find the eigenvalues of H for the case that it is not Hermitian and the case that it is Hermitian. That is V (x) = λδ(x + a) − λδ(x − a). (Start from the fact that ψ+Cφψ+Cφ ≥ 0 for any C. Plot the allowed energy 2 h ¯ bands on an energy axis assuming V0 = 2 eV and the spacing between atoms is 5 Angstroms.
4.287
18. Is ψ correctly normalized? Compute the expected value of x as a function of time by doing the integrals in the x representation.
2
. o b) Determine the coeﬃcients needed to satisfy the boundary conditions. By the uncertainty principle. 6.4
Homework 4
1. cos(φ) = cos(ka) +
2
ma2 V0 sin(ka) ka h ¯2
Assume that ma 2V0 = 3π and plot the constraint as a function of ka. the kinetic energy of an electron localized to that width is 2ma2 . 7. Assume the width of the square well h2 ¯ is a. The 1D model of a crystal puts the following constraint on the wave number k. At t = 0 a particle is in the one dimensional Harmonic Oscillator state ψ(t = 0) = √2 (u0 + u1 ). A beam of particles of energy E > 0 coming from −∞ is incident upon a double delta function potential in one dimension. Find the correctly normalized energy eigenfunction u5 (x) for the 1D harmonic oscillator.
Calculate ui xpuj by direct calculation. • Now do the same in the Heisenberg picture. note that since any energy eigenstate can be written as a series of raising operators times the d ground state. 5. show that Ah(A† )u0 = dh(A ) u0 . then the operator eiH is unitary. then the states U ui also form a complete set. An operator is Unitary if U U † = U † U = 1. that the states U ui are also orthonormal. 4. Calculate ui xuj and ui puj . What is the product ΔpΔx for this state? 3.5
Homework 5
1. At t = 0 a particle is in the one dimensional Harmonic Oscillator state ψ(t = 0) =
1 √ (u0 2
+ u1 ). Now calculate the same thing using
k
†
ui xuk uk puj . 8. we can represent A by dA† . that is U ψU φ = ψφ . Evaluate the “uncertainty” in x for the 1D HO ground state u0 xu0 . Similarly.288
18. Show that if the states ui form a complete set. Prove that a unitary operator preserves inner products. As a result of dA† this. 6. Show that if the states ui are orthonormal. evaluate the uncertainty in p for the ground state.
¨ • Compute the expected value of x as a function of time using A and A† in the Schrodinger picture. a 1D harmonic oscillator is in a linear combination of the energy eigenstates ψ= 2 u3 + i 5 3 u4 5
Find the expected value of p as a function of time using operator methods. At t = 0. u0 (x − x)2 u0 where x = ¯ ¯ 2.
. What is the product ΔpΔx? Now do the same for the ﬁrst excited state.
7. If h(A† ) is a polynomial in the operator A† . Show at if an operator H is hermitian.
The energy spectrum of hydrogen can be written in terms of the principal quantum number n to 2 μc2 be E = − α2n2 . The momentum operator conjugate to any cooridinate xi is h ∂xi .
5. noninteracting spin 1 particles are in a box. Rj ].
1 √ (u1 2
+ u3 ). At t = 0 a particle is in the one dimensional Harmonic Oscillator state ψ(t = 0) = Compute the expected value of x2 as a function of time. What are the energies (in eV) of the photons from the n = 2 → n = 1 transition in hydrogen and deuterium? What is the diﬀerence in photon energy between the two isotopes of hydrogen? 2. The number density of conduction electrons in copper is 8. 6. rj ] and [pi . Calculate the commutators of i the center of mass coordinates and momenta [Pi . 4.289
18. The volume of a nucleus is approximately 1. 3. Estimate the Fermi energy of the protons and neutrons separately.1A 3 Fermis. Two identical. N is the number of neutrons.6
Homework 6
1. What is the Fermi energy in electron volts? 7. where A = N + Z. Write down the full lowest energy wave 2 function for both particles with spin up and for one with spin up and the other spin down. Rj ] and of the internal coordinates and momenta [pi .5 × 1022 per cubic centimeter.
1
. Be sure your answer has the correct symmetry under the interchange of identical particles. A Lead nucleus consists of 82 protons and 126 neutrons. rj ]. and Z is the number of protons. Calculate the commutators [Pi . Calculate the Fermi energy of a gas of massless fermions with n particles per unit volume.
¯ ∂ 8. Prove that the operator that exchanges two identical particles is Hermitian.
A particle in a spherically symmetric potential has the wavefunction ψ(x.8 Fermis and zero potential outside.
≤ 2 in terms of the Cartesian coordinates x.
. y. Prove that L2 = L2 = 0 is only possible for x y 6. y.18 MeV. Assume that the potential is a spherical well with potential of −V0 for r < 2. z) = C(xy + yz + 2 zx)e−αr . a bound state of a proton and neutron with = 0. The Hamiltonian for a rotor with axial symmetry is H = x 1 y + 2Iz where the I are constant 2I 2 moments of inertia. What are the possible results and the probabilities of h each? If the measurement of L2 yields 6¯ 2 . Write the spherical harmonics for = 0. Determine and plot the eigenvalues of H for dumbbelllike case that I1 >> I2 . A particle is in the state ψ = R(r) L . 5.290
18.7
Homework 7
1 3 Y21
1. Find the expected values of
1 2 2. Calculate the matrix elements Y
m1 Lx Y m2
and Y
2 m1 Lx Y m2 L2 +L2 L2
4. A measurement of L2 is made. and Ly . The deuteron. what are the possilbe outcomes and what are the probabilities of each?
3. A particle is in the state ψ = R(r) 3 Y11 + i 3 Y10 . and z. Lz . what are the possible measured values of Lz and what are the corresponding probabilities? 8. Lx . Find the approximate value of V0 using numerical techniques.
7.
2
+i
1 3 Y20
−
1 3 Y22
. has a binding energy of 2. If a measurement of the x component of angular momentum is made.
2. Note that there is a good deal of degeneracy in this problem so the three lowest energies actually means 4 radial wavefunctions and 10 total states.nz .ny. φ). The diﬀerential equation for the 3D harmonic oscillator H = 2m + 1 mω 2 r2 has been solved in the 2 notes. You may write them in terms of the standard Y m but please write out the radial parts of the wavefunction completely. The nucleus (beta) decays suddenly into that of He3 .8
Homework 8
1. θ. Show that at large r. Calculate the probability that the electron remains in the ground state. A hydrogen atom is in the state ψ = 1 4ψ100 + 3ψ211 − ψ210 + 10ψ21−1 .
p 8. 5. Try to write the solutions ψ000 and ψ010 in terms of the solutions in cartesian coordinates with the same energy ψnx. Calculate the diﬀerence in wavelengths of the 2p to 1s transition in Hydrogen and Deuterium. What are the limits for ka large and small? 3. Use the recursion relations derived there to write out the wave functions ψn m (r. Tritium is a unstable isotope of Hydrogen with a proton and two neutrons in the nucleus. Calculate the = 0 phase shift for a hard sphere V = ∞ for r < a and V = 0 for r > a. using the same techniques as we used for Hydrogen.
2
.291
18. What is P (pz ). Assume an atom of Tritium starts out in the ground state. Calculate the = 0 phase shift for the spherical potential well for both and attractive and repulsive potential. φ) for the three lowest energies. √ 6. What are the possible 6 energies that can be measured and what are the probabilities of each? What is the expectation value of L2 ? What is the expectation value of Lz ? What is the expectation value of Lx ? 7. Calculate the wavelength of the 2p to 1s transition in positronium. 4. the radial ﬂux is large compared to the angular components of the ﬂux for ±ikr wavefunctions of the form C e r Y m (θ. the probability distribution of pz for the Hydrogen energy eigenstate ψ210 ? You may ﬁnd the expansion of eikz in terms of Bessel functions useful.
Given an unpolarized spin 1 beam of intensity I going into the following 2 SternGerlach apparati. Find the value of C that properly normalizes the state. At that instant.9
Homework 9
2
1. a measurement of the y component of the spin is made. What is the probability ¯ that the value − h will be found? 2
4. Consider a system of spin 1 . An electron in the Hydrogen potential V (r) = − er is in the state ψ(r) = Ce−αr .292
18. what intensity comes out? I→ I→ I→ I→ I→ + − + − + − + − + − →
z
→
z
+ − + − →
u
→?
x
→
z
→?
u
+ − + − + −
+ − + − + −
→?
z
→
z
→
u
→?
z
→
z
→
u
→?
x
. What are the eigenstates and eigenvalues of the operator Sx + Sy ? 2 Suppose a measurement of this quantity is made. What is the probability that the electron be found in the ground state of Hydrogen? 2. At that time it is 2 2 placed in a constant magnetic ﬁeld B in the z direction. Let’s deﬁne the u axis to be in the xz plane. Find its wave function in momentum space. What is the probability that a subsequent measurement of Sy yields h ? 2 5. the magnetic ﬁeld is very quickly switched to the x direction. An electron is in the ψ210 state of hydrogen. between the positive x and z axes and at an angle of 30 degrees to the x axis. The spin is allowed to precess for a time T . and the system is found to be in the eigenstate ¯ with the larger eigenvalue. A spin 1 particle is in an eigenstate of Sy with eigenvalue + h at time t = 0.
¯ 3. After another time interval T .
This will put a factor of 4 into Maxwell’s equations but not change physics. Similar tradeoﬀs can be made with the magnetic ﬁeld strength and the constant on the Lorentz force law. Maxwell’s Equations in CGS units are ∇·B 1 ∂B ∇×E + c ∂t ∇·E 1 ∂E ∇×B− c ∂t The Lorentz Force is = = = = 0 0 4πρ 4π J. there is the freedom to. c
In fact.
.
19. an even better deﬁnition (rationalized HeavisideLorentz units) of the charges and ﬁelds can be made as shown in the introduction to ﬁeld theory in chapter 31. Complements EV I .
μ0 J
These equations have needless extra constants (not) of nature in them so we don’t like to work in these units. we will study the interactions of electrons in an electromagnetic ﬁeld. We will show that a symmetry allowing us to change the phase of the electron wave function requires the existence of EM interactions (with the gauge symmetry). increase the ﬁeld by a factor of 2 but decrease the charge by a factor of 2 at the same time. c
1 F = −e(E + v × B). We will compute the additions to the Hamiltonian for magnetic ﬁelds. Since the Lorentz force law depends on the product of the charge and the ﬁeld.293
19
Electrons in an Electromagnetic Field
In this section. There are no extra constants other than π. DV II and HIII . The choices made in CGS units are more physical (but still not perfect). and in CohenTannoudji et al. These topics are covered in Gasiorowicz Chapter 13.1
Review of the Classical Equations of Electricity and Magnetism in CGS Units
You may be most familiar with Maxwell’s equations and the Lorentz force law in SI units as given below. ∇·B ∂B ∇×E+ ∂t ∇·E = = = 0 0 ρ
0
1 ∂E ∇×B− 2 = c ∂t F = −e(E + v × B). for example. For now we will stick with the more standard CGS version of Maxwell’s equations. Our textbook and many other advanced texts use CGS units and so will we in this chapter. The gauge symmetry exhibited in electromagnetism will be examined in quantum mechanics.
For time independent charge and current distributions. E × B gives rise to momentum density in the ﬁeld. makes sense. These greatly simplify the above wave equations in an obvious way.5.
19. the coulomb gauge. For time dependent conditions. is often used. The two results we want to use as inputs for our study of Quantum Physics are • the classical gauge symmetry and • the classical Hamiltonian. so this gauge symmetry will be important in quantum mechanics. A φ → A − ∇f (r. the Lorentz gauge.2
The Quantum Hamiltonian Including a Bﬁeld
We will quantize the Hamiltonian H= e 1 p+ A 2m c
2
− eφ
.5. as well as the usual force due to an electric ﬁeld. ∇ · A + 1 ∂φ = 0. t) → φ+ c ∂t
Note that when we quantize the ﬁeld. the potentials will play the role that wave functions do for the electron.2) the Lorentz Force from it. ∇ · A = 0. the classical Hamiltonian for electrons in an electromagnetic ﬁeld becomes H= 1 e p2 → p+ A 2m 2m c
2
− eφ
The magnetic force is not a conservative one so we cannot just add a scalar potential. 1 ∂ (∇ · A) = c ∂t 1 ∂φ 1 ∂2A −∇2 A + 2 2 + ∇ ∇ · A + = c ∂t c ∂t −∇2 φ − 4πρ 4π J c
These derivations (see section 19. c ∂t is often convenient. Finally.1) are fairly simple using Einstein notation. We know that there is momentum contained in the ﬁeld so the additional momentum term. Applying the second two equations we get wave equations in the potentials. The Maxwell equations are invariant under a gauge transformation of the potentials. The evidence that this is the correct classical Hamiltonian is that we can derive (see section 19. B E = ∇×A = −∇φ − 1 ∂A c ∂t
then the ﬁrst two Maxwell equations are automatically satisﬁed.294 If we derive the ﬁelds from potentials. t) 1 ∂f (r. The electron generates an Eﬁeld and if there is a Bﬁeld present. We can use the gauge symmetry to simplify our equations.
5.1: Splitting of orbital angular momentum states in a B ﬁeld. the ﬁrst term on the left side. and the second can be neglected. In atoms. 2mc
e where μ = − 2mc L. by replacing the momentum by the momentum operator. The charged particles are essentially free to move in the plasma. is particularly simple to calculate because the the hydrogen energy eigenstates are also eigenstates of the additional term in the Hamiltonian. for realizable magnetic ﬁelds.4×109 gauss compared to hydrogen binding energy). The additional magnetic ﬁeld terms are important in a plasma because the typical radii can be much bigger than in an atom.2). An estimate (see section 19. So. The computation (see section 19.295 in the usual way.5. On earth.4. The Zeeman splitting of Hydrogen states. Note that the electron spin which is not included here also contributes to the splitting and will be studied later.3) yields −¯ 2 2 h e2 e r2 B 2 − (r · B)2 ψ = (E + eφ)ψ. The second term may be important in very high magnetic ﬁelds like those produced near neutron stars or if distance scales are larger than in atoms like in a plasma (see example below). p is the variable conjugate to r and is related to the velocity by e p = mv − A c as seen in our derivation of the Lorentz force (See Section 19. the dominant additional term is the one we anticipated classically in section 17. the ﬁrst term is fairly small (down by a factor of 2.4. the correction can be calculated exactly and easily. Most regions of space contain plasmas and magnetic ﬁelds. for the case of a constant magnetic ﬁeld. ∇ ψ+ B · Lψ + 2m 2mc 8mc2 The usual kinetic energy term. neglecting electron spin. not just the particle’s momentum.5. We see two additional terms due to the magnetic ﬁeld. with spin included.
. the magnetic moment due to the electron’s orbital angular momentum. we have a quantum mechanics problem to solve.4) of the size of the two B ﬁeld terms for atoms B shows that.
The Zeeman eﬀect. for atoms. together to make a (usually) electrically neutral mix. eﬀectively. was a powerful tool in understanding Quantum Physics and we will discuss it in detail in chapter 22. has been recovered. this term gives rise to the Zeeman eﬀect: otherwise degenerate atomic states split in energy when a magnetic ﬁeld is applied. we use plasmas in magnetic ﬁelds for many things. A plasma is composed of ions and electrons. If we apply an external magnetic ﬁeld. The standard potential energy of an electron in an Electric ﬁeld is visible on the right side. Note that the momentum operator will now include momentum in the ﬁeld. Hence.*
The result is that the shifts in the eigenenergies are ΔE = μB Bm where m is the usual quantum number for the z component of orbital angular momentum. As this Hamiltonian is written. This is. including nuclear fusion reactors. * See Example 19. HB = e B · L = −μ · B.
In the ﬁrst solution we understand n in terms of the radial wavefunction in cylindrical coordinates and the angular momentum about the ﬁeld direction. We will now turn the remaining 1D part of the Schr¨dinger equation into the 1D harmonic oscillator equation. We will turn the radial equation into the equation we solved for Hydrogen.t) ψ(r. ψ → eiλ ψ.3
Gauge Symmetry in Quantum Mechanics
Gauge symmetry in Electromagnetism was recognized before the advent of quantum mechanics.4. we will use translational symmetry along the B ﬁeld direction as well as translational symmetry transverse to the B ﬁeld. t) → eiλ(r. t) changing the equation unless we do something else to cancel o the changes. the physical meaning is less clear. but what about the Schr¨dinger equation? It must also be unchanged. ¯ k is the conserved momentum along the ﬁeld direction which h can take on any value. In the second solution. t) 1 ∂f (r. This is a symmetry in the theory which we already know about. showing o that the two problems we have solved analytically are actually related to each other! * See Example 19.7) shows that the equation remains unchanged if we also transform the potentials A → A − ∇f (r.2: A neutral plasma in a constant magnetic ﬁeld. we will solve the Quantum Mechanics problem two ways: one using our new Hamiltonian with B ﬁeld terms. Its clear that this transformation leaves the absolute square of the wavefunction the same. Indeed. In the second solution. ψ(r. in quantum mechanics. We could call this global phase symmetry.5. The derivatives in the o Schr¨dinger equation will act on λ(r.
19. f (r. n is an integer dealing with the state in x and y. We have seen that symmetries play a very important role in the quantum theory. The ﬁrst one will exploit both rotational symmetry about the B ﬁeld direction and translational symmetry along the B ﬁeld direction. we can change the phase by a diﬀerent amount at each point in spacetime and the physics will remain unchanged. e 2 1 p + A ψ = (E + eφ)ψ 2m c A little calculation (see section 19. We know that the all observables are unchanged if we make a global change of the phase of the wavefunction. t) φ → φ+ c ∂t h ¯c λ(r. gauge symmetry can be seen as the basis for electromagnetism and conservation of charge. All relative phases (say for amplitudes to go through diﬀerent slits in a diﬀraction experiment) remain the same and no physical observable changes. 2me
which depends on 2 quantum numbers. and the other writing the Hamiltonian in terms of A.296 In the example below. This local phase symmetry is bigger than the global one. t) = e
. t). Let’s postulate that there is a bigger symmetry and see what the consequences are. t) That is.*
The result in either solution for the eigenenergies can be written as En = eB¯ h me c n+ 1 2 + h ¯ 2 k2 .
then we have a very useful relation between the gauge function and the vector potential in a ﬁeld free region. This of course is still consistent with B = 0. Integrating this equation. A = A − ∇f (r) = 0 Then the old vector potential is then given by A = ∇f (r).8) the quantization of magnetic ﬂux by calculating the line integral of A around a closed loop in a ﬁeld free region. It turns out that the weak and the strong interactions are also gauge theories and. Magnetic ﬂux is excluded from the superconducting region. t) φ → φ+ c ∂t e ¯ ψ(r. t) → e−i hc f (r. We can understand a number of them by looking at the vector potential in a ﬁeld free regions.
.
We can derive (see section 19. If we have a superconducting ring. we have a B=0 region surrounding some ﬂux. Make a gauge transformation such that A = 0.t) ψ(r. To be speciﬁc. We will write our standard gauge transformation in the traditional way to conform a bit better to the textbooks. have the next simplest possible gauge symmetries after the one in Electromagnetism.
r r
dr · A =
r0 r0
dr · ∇f = f (r) − f (r0 )
If we choose f so that f (r0 ) = 0. in some sense.5.
r
f (r) =
r0
dr · A. that the ﬂux going through a ring of superconductor is quantized. take our gauge transformation of the vector potential. but. t) 1 ∂f (r. We have shown then. Electromagnetism is called a o gauge theory because the gauge symmetry actually deﬁnes the theory. Φ= 2nπ¯ c h e
A good example of a B = 0 region is a superconductor. we can write the function f (r) in terms of A(r).297 This is just the standard gauge transformation of electromagnetism. A → A − ∇f (r. If B = 0 then A can be written as the gradient of a function f (r). t) There are measurable quantum physics consequences of this symmetry. we now see that local phase symmetry of the wavefunction requires gauge symmetry for the ﬁelds and indeed even requires the existence of the EM ﬁelds to cancel terms in the Schr¨dinger equation.
The Aharanov B¨hm Eﬀect brings us back to the two slit diﬀraction experiment but adds magnetic o ﬁelds. Φ= 2nπ¯ c h 2e
This is due to the pairing of electrons inside a superconductor.298
Flux is observed to be quantized but the charge of the particle seen is 2e. At the screen. the amplitudes from the two slits interfere
.
electron gun
1111111 0000000 1111111 0000000 flux 1111111 0000000 1111111 0000000
screen
The electron beams travel through two slits in ﬁeld free regions but we have the ability to vary a magnetic ﬁeld enclosed by the path of the electrons.
Let’s start with B = 0 and A = 0 everywhere. ψ1 ψ2 ψ → ψ1 e → ψ2 e =
e −i hc ¯ 1 e −i hc ¯ 2 e −i hc ¯
dr·A
dr·A
ψ1 e
−i eΦ hc ¯
dr·A
2
+ ψ2 e
The relative phase from the two slits depends on the ﬂux between the slits.4.4. When we change the B ﬁeld. Choosing the z axis so that the
In general. L2 and Lz . we have HZeeman = eBz Lz .
19. φ. however. While this may at ﬁrst seem amazing. eB e2 B 2 2 −¯ 2 2 h Lz ψ + ∇ ψ+ (x + y 2 )ψ = (E + eφ)ψ 2me 2me c 8me c2 The problem clearly has translational symmetry along the z direction and rotational symmetry around the z axis. 2μc
· L. ψ(r) = unmk (ρ)eimφ eikz
. By varying the B ﬁeld. The magnetic moment of the electron’ s spin greatly complicates the problem. things did not work our according to plan at all. We then have cylindrical symmetry and will work in the coordinates. we will shift the diﬀraction pattern even though B = 0 along the whole path of the electrons.2
A Plasma in a Magnetic Field
An important place where both magnetic terms come into play is in a plasma. In this case. we know that Lz and pz commute with the Hamiltonian and will give constants of the motion.4
19. There. We will solve this later. we have seen similar eﬀects in classical E&M with an EMF induced in a loop by a changing B ﬁeld which does not touch the actual loop.
19. (Hhydrogen + HZeeman )ψn
m
= (En + mμB B)ψn
m
This would be a really nice tool to study the number of degenerate states in each hydrogen level. our hydrogen states are eigenstates of H.1
Examples
The Naive Zeeman Splitting
e 2μc B
The additional term we wish to consider in the Hamiltonian is constant ﬁeld points in the z direction. Given the symmetry. many electrons are not bound to atoms and external Electric ﬁelds are screened out. When the experiment was done. the wavefunctions must change. the energy eigenstates we derived in the Hydrogen problem are still eigenstates of the full Hamiltonian H = Hhydrogen + HZeeman . ρ. and z. Let’s assume there is a constant (enough) B ﬁeld in the z direction. the addition of a new term to the Hamiltonian will require us to use an approximation to solve the problem.299 ψ = ψ1 + ψ2 . Remember. We therefore will be able to separate variables in the usual way.
ψ = v(x)eiky y eikz z Then we actually can use our harmonic oscillator solution instead of hydrogen! The energies come out to be eB¯ h 1 h ¯ 2 k2 .5
19.5) the energies the equation in ρ we may reuse the Hydrogen solution ultimately get E= eB¯ h me c n+ 1 + m + m 2 + h ¯ 2 k2 2m
and associated LaGuerre polynomials (as in Hydrogen) in ρ2 (instead of r).
19. y H = = 1 e p+ A 2me c 1 2me
2
=
1 2me
p2 + py + x eB c
2
eB x c
2
+ p2 z
p2 + p2 + x y
2eB xpy + c
x2 + p2 z
This Hamiltonian does not depend on y or z and therefore has translational symmetry in both x and y so their conjugate momenta are conserved.5.1
Derivations and Computations
Deriving Maxwell’s Equations for the Potentials
We take Maxwell’s equations and the ﬁelds written in terms of the potentials as input. The solution turns out to be simpler using the Hamiltonian written in terms of (see section 19.5. The right column uses the totally antisymmetric tensor in 3D ijk and assumes summation over repeated indices (Einstein notaton). So in this notation. dot products can be simply written as a · b = ai bi and any component of a cross product is written (a × b)k = ai bj ijk .6) A if we choose the right gauge by setting A = Bxˆ. In the left column the equations are given in the standard form while the right column gives the equivalent equation in terms of indexed components. ∇·B = 0 ∇×E + 1 ∂B =0 c ∂t ∂ Bi = 0 ∂xi ∂ 1 ∂Bk =0 Ej ijk + ∂xi c ∂t ∂ Ek = 4πρ ∂xk ∂ 4π 1 ∂Ek = Jk Bj ijk − ∂xi c ∂t c ∂ Bj = An mnj ∂xm ∂ 1 ∂Ak Ek = − φ− ∂xk c ∂t
∇ · E = 4πρ ∇×B− 4π 1 ∂E = J c ∂t c B =∇×A E = −∇φ − 1 ∂A c ∂t
.300 In solving (see section 19. En = n+ + me c 2 2me Neglecting the free particle behavior in z. We can use this symmetry to write the solution and reduce to a 1D equation in v(x). these are called the Landau Levels.5. This is an example of the equivalence of the two real problems we know how to solve.
Similarly we may work with the Gauss’s law equation ∇·E = ∂ ∂ Ek = − ∂xk ∂xk ∂ 1 ∂Ak φ+ = ∂xk c ∂t 1 ∂ (∇ · A) = −∇2 φ − c ∂t 4πρ 4πρ
For the fourth equation we have. We only have a nonzero term if j = 3 so the other 2 terms in the sum are zero. ∂ 4π 1 ∂Ek = Jk Bj ijk − ∂xi c ∂t c ∂ 1 ∂ 1 ∂Ak 4π Jk φ+ = ijk + c ∂t ∂xk c ∂t c
∂ ∂ An ∂xi ∂xm
mnj
Its easy to derive an identity for the product of two totally antisymmetric tensors mnj ijk as occurs above. For the second equation.301 If the ﬁelds are written in terms of potentials. we write it out in terms of the potentials and notice that the ﬁrst term ∂ ∂ ∂xi ∂xj φ ijk = 0 for the same reason as above. we must have either m = 1 and n = 2 or vice versa. ∇·B = ∂ ∂ ∂ Bi = An ∂xi ∂xi ∂xm
mni
=
∂ ∂ An ∂xm ∂xi
mni
We could also just interchange the index names i and m then switch those indices around in the antisymmetric tensor. ∂ Ej ∂xi
ijk
+
1 ∂Bk c ∂t
= = =
−
∂ ∂ 1 ∂Aj 1 ∂ ∂ φ+ An ijk + ∂xi ∂xj c ∂t c ∂t ∂xm ∂ ∂Aj 1 ∂ ∂An ijk + mnk c ∂xi ∂t ∂xm ∂t 1 ∂ ∂Aj ∂ ∂Aj =0 ijk + ijk c ∂xi ∂t ∂xi ∂t
mnk
The last step was simply done by renaming dummy indices (that are summed over) so the two terms cancel.
mnj ijk
=
mnj kij
= (δkm δin − δkn δim )
. All the indices of any tensor have to be diﬀerent in order to get a nonzero result. But if j = 3. So we can write. We also must not have i = k since all the indices have to be diﬀerent on each epsilon. ∂ ∂ ∂ ∂ ∇·B = An inm = − An mni ∂xm ∂xi ∂xm ∂xi We have the same expression except for a minus sign which means that ∇ · B = 0. Since the j occurs in both tensors (and is summed over) we can simplify things. Lets verify the ﬁrst equation by plugging in the B ﬁeld in terms of the potential and noticing that we can interchange the order of diﬀerentiation. Take the case that i = 1 and k = 2. then the ﬁrst two Maxwell equations are automatically satisﬁed.
∂ ∂ 1 ∂ 2 Ak ∂ ∂ 1 ∂ ∂φ 4π + 2 Jk Ai − Ak + = 2 ∂xi ∂xk ∂xi ∂xi c ∂xk ∂t c ∂t c 1 ∂ 2 Ak ∂ 1 ∂ ∂φ 4π + 2 Jk = ∇ · A − ∇2 Ak + 2 ∂xk c ∂xk ∂t c ∂t c 1 ∂φ 1 ∂ 2 Ak ∂ 4π ∇·A+ Jk −∇2 Ak + 2 = c ∂t2 ∂xk c ∂t c −∇2 A + 1 ∂φ 1 ∂2A +∇ ∇·A+ c2 ∂t2 c ∂t = 4π J c
The last two equations derived are wave equations with source terms obeyed by the potentials. The momentum conjugate to r includes momentum in the ﬁeld.
19. they can be simpliﬁed with a choice of gauge. dpi dvi e dAi =m − dt dt c dt. Hamilton’s equations are q ˙ p ˙ = = ∂H ∂p ∂H − ∂q
where q ≡ r and the conjugate momentum is already identiﬁed correctly p ≡ p.2
The Lorentz Force from the Classical Hamiltonian
In this section. we wish to verify that the Hamiltonian H= 1 e p+ A 2m c
2
− eφ
gives the correct Lorentz Force law in classical physics.
.5. As discussed in the opening section of this chapter. we have ˙ dr dt mv p = 1 e p+ A m c e = p+ A c e = mv − A c
Note that p = mv. we get. We will then proceed to use this Hamiltonian in Quantum Mechanics. Remember that these are applied assuming q and p are independent variables. Beginning with q = ∂H/∂p. We now time diﬀerentiate this equation and write it in terms of the components of a vector.302 Applying this identity to the Maxwell equation above.
303
∂H Similarly for the other Hamilton equation (in each vector component) pi = − ∂xi . So this is the right Hamiltonian for an electron in a electromagnetic ﬁeld. c ∂xi
Fi = mai = −eEi +
Let’s work with the other two terms to see if they give us the rest of the Lorentz Force. We now have two equations for hand sides yielding
dpi dt
derived from the two Hamilton equations. We equate the two right
mai = m
e ∂A dvi ∂φ e dAi e =− . we have ˙ dpi dt e = pi = − mc p + e A · ˙ c ∂A ∂xi
+ e∂φ
∂xi . v×B = −vj Q. we will expand the expression using the totally antisymmetric tensor. e e ∂Ai ∂φ = −eEi + ∂xi c ∂t ∂A e −v · + v · ∇ Ai . Fi = −eEi − So we have = v× ∇×A = vj ∂An ∂An εmnk εjki = vj (εmnk εjki ) ∂xm ∂xm ∂Aj ∂Ai − ∂xi ∂xj . +e + mc ∂xi ∂xi c dt
mai = −
The total time derivative of A has one part from A changing with time and another from the particle moving and A changing in space. e c v · ∇ Ai − v · ∂A ∂xi = ∂ ∂Aj e Ai − vj vj c ∂xj ∂xi ∂Aj ∂Ai − ∂xi ∂xj ∂Ai ∂Aj e − = vj c ∂xj ∂xi
We need only prove that v×B
i
= vj
.D. +e + c ∂xi ∂xi c ∂t c We notice the electric ﬁeld term in this equation.
i
i
∂An ∂An (εmnk εjik ) = −vj (δmj δni − δmi δnj ) = +vj ∂xm ∂xm
. ∂A dA = + v·∇ A dt ∂t so that ∂A e e ∂φ e ∂Ai Fi = mai = − v · + v · ∇ Ai .E. +e + p+ A · dt mc c ∂xi ∂xi c dt ∂A e ∂φ e dAi (mv) · . We now need to quantize it.
To prove this. e v×B c i which is the Lorentz force law.
Substituting back.304 19. The ﬁrst one is the magnetic moment term we have already used and the second will be negligible in atoms.
We see that there are two new terms due to the magnetic ﬁeld. we get e2 e −¯ 2 2 h ∇ ψ+ B · Lψ + r2 B 2 − r · B 2μ 2μc 8mc2
2
ψ = (E + eφ) ψ. ∂ψ ∂ψ r × B · ∇ψ = ri Bj εijk = −Bj ri εikj ∂xk ∂xk r×B
2 2
ψ = (E + eφ) ψ
i = −B · r × ∇ψ = − B · Lψ h ¯
= =
ri Bj εijk rm Bn εmnk = (ri Bj ri Bj − ri Bj rj Bi ) r2 B 2 − r · B
2
−0
So. o 1 2μ
e 1 p+ A 2μ c
2
− eφ
h ¯ e ∇+ A · i c
h ¯ e ∇ψ + Aψ i c
= = =
(E + eφ) ψ (E + eφ) ψ (E + eφ) ψ
−¯ 2 2 h ie¯ h e2 ie¯ h ∇ ψ− ∇ · Aψ − A · ∇ψ + A2 ψ 2μ 2μc 2μc 2mc2 −¯ 2 2 h ie¯ h e2 ie¯ h ∇ ψ− ∇·A ψ− A · ∇ψ + A2 ψ 2μ 2μc μc 2mc2 The second term vanishes in the Coulomb gauge i. we choose the vector potential
since ∇×A
k
∂ 1 ∂ Aj εijk = − (xm Bn εmnj ) εijk ∂xi 2 ∂xi 1 1 = − δim Bn εmnj εijk = − Bn εinj εijk 2 ⎛ 2 ⎞ ⎛ = = 1 Bn ⎝ 2 εijn εijk ⎠ =
i j
⎞ ε2 ⎠ = Bk ijk
j
1 Bk ⎝ 2
i
it gives the right ﬁeld and satisﬁes the Coulomb gauge condition. plugging these two equations in.e. ∇ · A = 0.
. so −
h ¯2 2 e2 ie¯ h ∇ ψ− A · ∇ψ + A2 ψ = (E + eφ) ψ 2μ μc 2mc2 1 A=− r×B 2
Now for constant Bz .3 The Hamiltonian in terms of B
Start with the Hamiltonian H= Now write the Schr¨dinger equation..5. we obtain −¯ 2 2 h e2 ie¯ h r×B ∇ ψ+ r × B · ∇ψ + 2μ 2μc 8mc2 Now let’s work on the vector arithmetic.
φ. Lz ] = 0.
e2 h ¯c
a0 =
h ¯ αmc
2
19. h ¯ ∂ ψ = m¯ ψ h = i ∂φ h ¯ ∂ ψ = hkψ ¯ = i ∂z m2 ∂2u 1 ∂u imφ ikz e = −k 2 ψ − 2 ψ + 2 eimφ eikz + e ρ ∂ρ ρ ∂ρ 2me E eBm − k2 u = 0 − h ¯c h ¯2
4me c eB¯ h
d2 u 1 du m2 e2 B 2 − 2 u − 2 2 ρ2 u + + 2 dρ ρ dρ ρ 4¯ c h Let x =
eB 2¯ c ρ h
(dummy variable. Then ∇2 =
From the symmetry of the problem.4 The Size of the B ﬁeld Terms in Atoms
In the equation −¯ 2 2 h e2 e ∇ ψ+ B · Lψ + r2 B 2 − r · B 2μ 2μc 8mc2 the second term divided by (e2 /a0 ) e B · L/(e2 /a0 ) ∼ 2μc = = e B (m¯ ) /(e2 /a0 ) h 2μc αeBa0 αa2 m / e2 /a0 = m 0 B 2 2e 2 0.5 × 10−8 cm B =m mB −10 ) (2)(137) (4.8 × 10−10 ) 10 gauss 2μc
2
2
ψ = (E + eφ) ψ. These variables will be constants of the motion and we therefore choose ψ (r) Lz ψ pz ψ ∇2 ψ = umk (ρ) eimφ eikz . pz ] = [H. z.5. we can guess (and verify) that [H.5.8 × 10 5 × 109 gauss α= Divide the third term by the second:
e 0.5 × 10−8 B 2 a2 8mc2 a2 B 0 = α 0B = = 10 e B¯ h 4e (4)(137) (4. Then
d2 u 1 du m2 − 2 u − x2 u + λ = 0 + dx2 x dx x
. not the coordinate) and λ =
E−
h2 k 2 ¯ 2me
− 2m.5
Energy States of Electrons in a Plasma I eB e2 B 2 h ¯2 2 Lz ψ + x2 + y 2 ψ = Eψ ∇ ψ+ 2me 2me c 8me c2 1 ∂2 ∂2 ∂2 1 ∂ + 2 2 + 2+ 2 ∂z ∂ρ ρ ∂ρ ρ ∂φ
−
For uniform B ﬁeld.305 19. cylindrical symmetry ⇒ apply cylindrical coordinates ρ.
nr = 0 Max when ⇒ L0 = const ⇒ ψ2 ∼ e−x x2m
2
2 2 dψ2 = 0 = −2xe−x x2m + 2me−x x2m−1 dx
. The equations are the same if WE set our Recall that our λ =
4me c eB¯ h
E− ⇒
h2 k 2 ¯ 2me
= nr + 1+m 2
where nr = 0. nr We can localize electrons in classical orbits for large E and nr ≈ 0. 1. dy 2x dx Transforming the equation we get d2 G + dy 2 m + 1 −1 y dG λ − 2 − 2m + G = 0. This is the classical limit.306 In the limit x → ∞. . the eigenfunctions are G(y) = Lm (y).
− 2m. This gives us the energy eigenvalues h ¯ 2 k2 eB¯ h = 2me me c nr + 1 + m + m 2 .
d2 u − x2 u = 0 dx2
⇒
u ∼ e−x
2
/2
d2 u 1 du m2 − 2u=0 + dx2 x dx x ⇒ s2 = m 2
Try a solution of the form xs . . .. Then s(s − 1)xs−2 + sxs−2 − m2 xs−2 = 0 A well behaved function ⇒ s ≥ 0 ⇒ s = m u(x) = xm e−x Plugging this in.
E−
As in Hydrogen. 2. dy 4y
Compare this to the equation we had for hydrogen d2 H + dρ2 2 +2 −1 ρ dH λ−1− + H =0 dρ ρ
λ 4
with λ = nr + +1. we have d2 G + dx2 2m + 1 − 2x x dG + (λ − 2 − 2m) G = 0 dx
2
/2
G(x)
We can turn this into the hydrogen equation for y = x2 and hence dy = 2x dx d 1 d = . while in the other limit x → 0.
We can treat pz and py as constants of the motion and solve the problem in Cartesian coordinates! The terms in x and py are actually a perfect square. ψ = v(x)eiky y eikz z 1 2me −¯ 2 h d2 + dx2 1 me 2 eB c eB me c
2
x+
2
h ¯ cky eB h ¯ cky eB
2
v(x)
2
=
E− E−
h 2 ¯ 2 kz 2me h 2 ¯ 2 kz 2me
v(x)
−¯ 2 d2 h + 2me dx2
x+
v(x)
=
v(x)
This is the same as the 1D harmonic oscillator equation with ω = 1 2 h ¯ eB me c 1 2 h 2 ¯ 2 kz 2me
eB me c
¯ and x0 = − hck .
m¯ c h Be .5.6
Energy States of Electrons in a Plasma II
We are going to solve the same plasma in a constant B ﬁeld in a diﬀerent gauge.5 × 10−6 m cm (4. py ] = [H.8 × 10−10 esu) (2 × 104 g)
ρ=
This can be compared to the purely classical calculation for an electron with angular momentum m¯ h which gives ρ = ﬁeld. Bx. We can then compute H for a constant B ﬁeld in the z direction. H = 1 e p+ A 2me c 1 2me
2
=
1 2me
p2 + py + x eB c
2
eB x c
2
+ p2 z
=
p2 + p2 + x y
2eB xpy + c
x2 + p2 z
With this version of the same problem.05 × 10−27 erg sec) m ≈ 2. Then cm √ 2 3 × 1010 sec (1. pz ] = 0. ˆ ˆ ∂x
This A gives us the same B ﬁeld. we have [H. eB
E=
n+
h ¯ω =
n+
+
.
This simple calculation neglects to count the angular momentum stored in the
19. 0).307
1/2
m = x2
⇒
ρ=
2c h ¯m eB
Now let’s put in some numbers: Let B ≈ 20 kGauss = 2 × 104 Gauss. If A = (0. then B =∇×A= ∂Ay z = Bz.
t) ψ(r. ψ(r. (Note that an electron could be circulating about any ﬁeld line so there are many possible states. we can change the phase by a diﬀerent amount at each point in spacetime and the physics will remain unchanged.t) ψ(r. t) ¯ i c c e e h ¯ ∇ + A + ΔA + h∇λ(r.)
19. e 2 p + A ψ = (E + eφ)ψ c So let’s postulate the following transformation then see what we need to keep the equation invariant. The resulting states are somewhat strange and are not analogous to the classical solutions. t) → eiλ(r. The Schr¨dinger o must also be unchanged. We know that the absolute square of the wavefunction is the same. t) A → A + ΔA φ → φ + Δφ
We now need to apply this transformation to the Schr¨dinger equation.t) = eiλ(r.5.t) i¯ h i¯ h
∂λ(r. the convention being set before quantum mechanics. ψ(r.t) ψ =
i¯ h
∂ + eφ + eΔφ eiλ(r. t) ∂ + eφ + eΔφ − ¯ h ∂t ∂t ψ
ψ
ψ
∂λ(r. t) ∂ + eφ + eΔφ − ¯ h ∂t ∂t
Its easy to see that we can leave this equation invariant with the following choices. just in case you are worrying about the choice of ky and x0 and counting states. We now rewrite the gauge transformation in the more conventional way. t) That is.308 So we get the same energies with a much simpler calculation.t) i∇λ(r. Note that ∇eiλ(r. t) e ∂t
We can argue that we need Electromagnetism to give us the local phase transformation symmetry for electrons.
.t) ψ ∂t
Now we will apply the diﬀerential operator to the exponential to identify the new terms. ΔA Δφ = − = h ¯c ∇λ(r. o h ¯ e e ∇ + A + ΔA i c c
2
eiλ(r. t) → eiλ(r. eiλ(r. t) e h ¯ ∂λ(r. t). t) ¯ i c c
2
ψ
2
= =
eiλ(r.7
A Hamiltonian Invariant Under Wavefunction Phase (or Gauge) Transformations
We want to investigate what it takes for the Hamiltonian to be invariant under a local phase transformation of the wave function.t) h ¯ e e ∇ + A + ΔA + h∇λ(r.
t) φ → φ+ c ∂t h ¯c λ(r.8 Magnetic Flux Quantization from Gauge Symmetry
We’ve shown that we can compute the function f (r) from the vector potential.t) ψ(r.5. t) → eiλ(r. f (r.309
ψ(r. ψ does have to be single valued. but.
B field
path 1
r
0
r
path 2
Consider two diﬀerent paths from r0 to r. Now f is not a physical observable so the f1 − f2 does not have to be zero. t) = e A 19. as shown. If we take a ring of superconductor. ψ1 = ψ2 e e ¯ ¯ ⇒ e−i hc f1 = e−i hc f2 e (f1 − f2 ) = 2nπ ⇒ h ¯c 2nπ¯ c h ⇒ Φ = f1 − f2 = e
.
r
f (r) =
r0
dr · A
A superconductor excludes the magnetic ﬁeld so we have our ﬁeld free region. we get a condition on the magnetic ﬂux through the center. t) → A − ∇f (r. f1 (r) − f2 (r) = dr · A = dS · ∇ × A = dS · B = Φ
The diﬀerence between the two calculations of f is the ﬂux. t). t) 1 ∂f (r.
Note that the ﬁelds must be evaluated at the position of the electron. t) + 2mc σ · B(r.
19. The vector potential is given by A = (−yB. The Hamiltonian for an electron in a electromagnetic ﬁeld can be written as H = 2m [p + e e¯ h 2 c A(r. A charged particle is in an external magnetic ﬁeld. What are the constants of the motion? Prove that these are constants by evaluating their commutator with the Hamiltonian. Show that this can be written as the Pauli Hamiltonian
H=
e 1 σ · [p + A(r. xB/2. Calculate the wavelengths of the three Zeeman lines in the 3d → 2p transition in Hydrogen atoms in a 104 gauss ﬁeld. The vector potential is given by A = (0. B) with the gauge chosen so that A = (−yB. 0. Show that the Hamiltonian H = 2μ [p + e A(r. t).310 The ﬂux is quantized. Consider the problem of a charged particle in an external magnetic ﬁeld B = (0.
19. 0.7
Sample Test Problems
1. t).
1 6. Gauge symmetry was noticed in electromagnetism before the advent of Quantum Mechanics. 0) can represent the same physical situation? Why do the solutions look so diﬀerent? 5. Magnetic ﬂux is observed to be quantized in a region enclosed by a superconductor. This means that the total time derivative of A must also account for the motion of the electron. 0). xB.6
Homework Problems
1 1. A charged particle is in an external magnetic ﬁeld. t) yields the Lorentz force law for an c electron.
2. the fundamental charge seen is 2e. Show that the probability ﬂux for system described by the Hamiltonian H= is given by j= 2ie h ¯ [ψ ∗ ∇ψ − (∇ψ ∗ )ψ + Aψ ∗ ψ]. What is the symmetry transformation for the wave function of an electron from which the gauge symmetry for EM can be derived?
. 0). What are the constants of the motion? Prove that these are constants by evaluating their commutator with the Hamiltonian. 2. 3. What are the constants of the motion? Go as far as you can in solving the equations of motion and obtain the energy spectrum.
4. Use the energy eigenstates as the basis states. 0) and A = (0. xB. however. Can you explain why the same problem in the gauges A = (−yB/2. 2iμ h ¯c
∂(ψ ∗ ψ) ∂t
e 1 [p + A]2 2μ c
Remember the ﬂux satisﬁes the equations
+ ∇j = 0. t)]2 − eφ(r. 0. t)] 2m c
2
− eφ(r. Calculate the top left 4 × 4 corner of the matrix representation of x4 for the harmonic oscillator. 3. t)] − eφ(r. 0).
One of our ﬁrst uses of this will be to add the orbital angular momentum in Hydrogen to the spin angular momentum of the electron. These product states are eigenstates of total Sz but not necessarily of total S 2 . The states and their Sz eigenvalues are given below. They are independent variables except that the overall wave functions for identical particles must satisfy the (anti)symmetrization requirements. This will also be the case for the spin coordinates.1) the total spin operators obey the same commutation relations as individual spin operators h [Si . Its easy to show (see section 20. in CohenTannoudji et al. As with the combination of independent spatial coordinates. The sum of angular momentum will be quantized in the same way as orbital angular momentum. These products just mean. This material is covered in Gasiorowicz Chapter 15. we can make product states to describe the spins of two particles.
20. [S(1)i .311
20
Addition of Angular Momentum
Since total angular momentum is conserved in nature. Product State (1) (2) χ+ χ+ (1) (2) χ+ χ− (1) (2) χ− χ+ (1) (2) χ− χ− Total Sz eigenvalue h ¯ 0 0 −¯ h
. The exceptions will be when we apply external Fields which break the rotational symmetry. we will ﬁnd that eigenstates of the total angular momentum operator are usually energy eigenstates. We must therefore learn how to add diﬀerent components of angular momentum together. audio This is a very important result since we derived everything about angular momentum from the commutators.8. x(2)j ] = 0. for example. There are four possible (product) spin states when we combine two spin 1 2 particles. Sj ] = i¯ ijk Sk . the spin of particle 1 is up and the spin of particle 2 is down.1
Adding the Spins of Two Electrons
The coordinates of two particles commute with each other: [p(1)i . Chapter X and very brieﬂy in Griﬃths Chapter 6. S(2)j ] = 0 We deﬁne the total spin operators S = S(1) + S(2) . J = L+S audio Our results can be applied to the addition of all types of angular momentum.
these are all still eigenstates of S(1) and S(2) .3) that they are indeed the correct eigenstates. audio J J
2
= L+S = L2 + 2L · S + S 2 1 2 h ¯2 = (J − L2 − S 2 ) → (j(j + 1) − ( + 1) − s(s + 1)) 2 2
L·S
. We expect to be able to form eigenstates of S 2 from linear combinations of these four states. The s = 1 multiplet has three component states.2
Total Angular Momentum and The Spin Orbit Interaction
The spinorbit interaction (between magnetic dipoles) will play a role in the ﬁne structure of Hydrogen as well as in other problems.m=0 = = = = χ+ χ+ 1 √ χ(1) χ(2) + χ(1) χ(2) + − − + 2 χ− χ− 1 √ χ(1) χ(2) − χ(1) χ(2) + − − + 2
(1) (2) (1) (2)
audio As a necessary check. They 2 2 are still spin 1 and hence. Note that by deciding to add the spins together.8.8. We can use the lowering operator to derive (see section 20. (some of) the above 2 states are not eigenstates of S(1)z and S(2)z . It is a good example of the need for states of total angular momentum. The additional term in the Hamiltonian is HSO = Ze2 L · S 2m2 c2 r3
If we deﬁne the total angular momentum J in the obvious way we can write L · S in terms of quantum numbers.
20.m=0 χs=1. χs=1. we could not change the nature of the electrons. two of which are obvious from the list above. however. This will prove to be a general feature of adding angular momenta. Our states of deﬁnite total angular momentum and z component of total angular momentum will still also be eigenstates of the individual angular momenta squared.m=−1 χs=0.312 audio Verify the quoted eigenvalues by calculation using the operator Sz = S(1)z + S(2)z .2) the other eigenstates of S 2 . we can guess that we can make one s = 1 multiplet plus one s = 0 multiplet. we operate on these states with S 2 and verify (see section 20.m=1 χs=1. From pure counting of the number of states for each Sz eigenvalue.
The negative m states are symmetric with the positive ones. For example if we add a vector of length 3 to a vector of length 0. and apply the lowering operator 1 to ﬁnd the rest of the multiplet with j = + 2 . they are going to be the true energy eigenstates.7.4) by operating with J 2 . First lets argue that this makes sense when 2 2 2 we are adding two vectors. that the total angular momentum quantum number has two possible values j = + 1 or j = − 1 .* 2 As in the last section. Y χ+ . where N is the principal quantum number and will often be omitted. We can also count states for each eigenvalue of Jz as in the following examples.
20. * See Example 20.313 Since our eigenstates of J 2 and Jz are also eigenstates of L2 and S 2 (but not Lz or Sz ).* 2 * See Example 20. We can work the problem in general. L refers to the orbital angular momentum
.5. These equations will be applied when we calculate the ﬁne structure of Hydrogen and when we study the anomalous Zeeman eﬀect. we will only have the half integers allowed.8. We know that each eigenstate of J 2 and Jz will be a linear combination of the two product states with the right m. We can show in several 2 ways that.1: Counting states for = 3 plus spin 1 . only j = 1 is allowed. s is the total spin quantum number ((2s + 1) is the number of spin states).2: Counting states for any plus spin 1 . rather than a continuous range.
20. we could start with the highest Jz state.3
Adding Spin
1 2
to Integer Orbital Angular Momentum
Our goal is to add orbital angular momentum with quantum number to spin 1 . So these two values make sense physically. these are ideal for computing the spin orbit interaction. The general form is N 2s+1 Lj . This works well for some speciﬁc but is hard to generalize. For = 0. for = 0. It is essentially a standard way to write down the angular momementum quantum numbers of a state. Also we know that the quantum numbers like are not exactly the length of the vector but are close.5 For quantized angular momentum. ψ( ψ(
+ 1 )(m+ 1 ) 2 2 − 1 )(m+ 1 ) 2 2 m χ+
+ βY
(m+1) χ−
= =
+m+1 −m Y m χ+ + Y 2 +1 2 +1 −m +m+1 Y m χ+ − Y 2 +1 2 +1
(m+1) χ−
(m+1) χ−
We have made a choice in how to write these equations: m must be the same throughout.4
Spectroscopic Notation
A common way to name states in atomic physics is to use spectroscopic notation. ψj(m+ 1 ) = αY 2 audio The coeﬃcients α and β must be determined (see section 20. In fact. the resulting vector could take on a length between 2. as rotational symmetry tells us they must.7.5 and 3.
These are: 1 2S 1 2 2S 1 2 2P 3 2 2P 1 3 2S 1 3 2P 3 3 2P 1 3 2D 5 2 2 2 2 2 2 2 2
3 3 2D 2 4 2S 1 4 2P 3 4 2P 1 4 2D 5 4 2D 3 4 2F 7 4 2F 5 .
. Just like the z component of one vector can never be as great as the full vector length in QM.314 quantum number but is written as S. because of the uncertainty principle. P. 5. D. . .
20. 1. 6. 3. and j is the total angular
A quick example is the single electron states. in agreement with our classical vector model.3: Adding = 4 to = 2.7. 2 2 2 2 2 2 2
All of these have the presuperscript 2 because they are all spin onehalf. F. The vector model qualitatively explains the limits. . as we ﬁnd in Hydrogen. j takes on every value between the maximum an minimum in integer steps. Quantum Mechanics tells up that the result is quantized and that. Lets work one more. For atoms with more than one electron. for momentum quantum number.l 2 l2 l1 + l 2
In general. audio
l2 l2 l1 l1 .5
General Addition of Angular Momentum: The ClebschGordan Series
We have already worked several examples of addition of angular momentum. There are two j values for each . the total spin state has more possibilities and perhaps several ways to make a state with the same quantum numbers. .. 4. the two vectors can never quite achieve the maximum allowed classically. * See Example 20. is multiplets with j = 2. 2.5) that the number of states agrees with the number of product states. We can check (see section 20. . .8.*
The result. 3. . . 
1
−
2
≤j≤
1
+
2
The maximum and minimum lengths of the sum of the vectors makes sense physically. = 0.
The triplet state is symmetric under interchange. we will be interested in the symmetry under interchange of the angular momentum state. 2S .315 We have been expanding the states of deﬁnite total angular momentum j in terms of the product states for several cases.5: The parity of the pion from πd → nn. like two electrons in an atom.7
20. In the language of group theory. We have computed some of them here by using the lowering operator and some by making eigenstates of J 2 . The highest total angular momentum state. Lets use the combination of two spin 1 particles as an example.* * See Example 20. We know that we get total spin states of s = 1 and 2 s = 0. in this case. For example.
. for identical particles.*
20. if we add two spin 2 states together. will always be symmetric under interchange. The s = 0 state is called a singlet. with two terms. We can have any combination of these states.7. the symmetry of the angular momentum wave function will alternate.6
Interchange Symmetry for States with Identical Particles
If we are combining the angular momentum from two identical particles. m = s. The s = 1 state is called a triplet because there are three states with diﬀerent m values. (1) (2) χ11 = χ+ χ+ . when we take the direct product of two representations of the the SU(2) group we get: 5 ⊗ 5 = 9S ⊕ 7A ⊕ 5S ⊕ 3A ⊕ 1S where the numbers are the number of states in the multiplet. We can see this by looking at the highest m state. the result remains symmetric under interchange. we must choose a state orthogonal to the symmetric state and this will always be antisymmetric. beginning with a symmetric state for the maximum total angular momentum. There are two diﬀerent eigenstates of Sz for spin 1 .4: Two electrons in a P state. 1A and 0S . both spins to have the maximum z component. So the product state has just one term and it is symmetric under interchange. When we lower this state with the (symmetric) lowering operator S− = S(1)− + S(2)− . The general expansion is called the ClebschGordan series: ψjm =
m1 m2 1 m1 2 m2 jm 1 2
Y
1 m1
Y
2 m2
or in terms of the ket vectors jm
1 2
=
m1 m2
1 m1 2 m2 jm 1 2
 1 m1 2 m2
The ClebschGordan coeﬃcients are tabulated. To get the maximum m.7. 3A . the resulting states are: 4S . s = s1 + s2 . To make the next highest state.
20. In fact. implying 2 × 7 = 14 possible product states like 2 Y31 χ+ .7.1
Examples
Counting states for = 3 Plus spin
1 2
For = 3 there are 2 + 1 = 7 diﬀerent eigenstates of Lz . * See Example 20.
j = ± 1 .
20.3
Adding
= 4 to
=2
As an example.
20.1) (3.1) (2. leaving 2 (4 + 2) − (2 + 2) = 2 = 2 − 1 2 +1
Thus we have a state with j = −
1 2
and that’s all.2) (3. while for spin we have 2 states χ± .0) (1.0) (4.2) (1.2) (3. that is 6 and 8 states respectively.1) (0. This makes up (2j + 1) = (2 + 2) states. Hence the composite system has 2(2 + 1) states total.0) (3. and j = 2 state. This makes sense in the vector model. 
1
−
2
≤j≤
1
+
2
and that j takes on every integer value between the limits.0) (2. Since 6 + 8 = 14 this gives us the right number of states.2) (2. audio Total m 6 5 4 3 2 1 0 1 2 3 4 5 6 (m1 .0) (2.316 We will argue based on adding vectors.1) (0. Now the highest m value left is 5.2) (0. m2 ) (4.2) (1..2) (0. we count the states for each value of total m (z component quantum number) if we add 1 = 4 to 2 = 2. there are (2 + 1) diﬀerent m states.1) (4.1) (2.1) (2. and uses up the states at each value of m.1) (2.2) (2.2) (1.7. Max jz = +
1 2
so we have a state with j = + 1 . so a j = 5 states uses up a state at each m value between 5 and +5..1) (1.1) (2.2) (4.0) (4.2) (3. that there will be two total angular momentum states that can be made up from the 14 product states. This uses up all the states. Each of these has 2 2 2 2j + 1 states.1) (4.2) (2.0) (3.0) (3. Similarly we ﬁnd a j = 4.2) (1.1) (4.1) (3.2)
Since the highest m value is 6.2
Counting states for Arbitrary
Plus spin
1 2
For angular momentum quantum number .2) (1.1) (3.7.2) (0.1) (4.2) (1.
. So we ﬁnd in this case.0) (1.1) (3.2) (4.1) (1. in this case j = 5 and j = 7 .1) (4. we expect to have a j = 6 state which uses up one state for each m value from 6 to +6. j = 3.
s1 . 2. j. the = 2 and = 0 states are symmetric. lets note the symmetry of each of the above states. 1. s2 . The maximum allowed state will always need to be symmetric in order to achieve the maximum. . Our two electrons each have ell = 1 (P state) and s = momenta together to get the total. while the = 1 state is antisymmetric. 3 P2 D2 S0
1 1
Each atomic state will have the angular momentum quantum numbers
1.5 audio
The parity of the pion from πd → nn. allowing us to treat only the valence electrons. 
1
−
2
≤ s
≤
1
+
2
= 0. As can be seen above. In the atomic physics section. we will even deal with more than two electrons outside a closed shell. for example. 2 = 0. Examples of atoms like this would be Carbon.317 20.4 Two electrons in an atomic P state
If we have two atomic electrons in a P state with no external ﬁelds applied. 1
These states have a deﬁnite symmetry under interchange.
20. it is most useful to add L1 + L2 = L and S1 + S2 = S then to add these results L + S = J. 2 2 s=0 j=2 0 s=0 j=0
3
P0 . We will learn later that closed shells in atoms (or nuclei) have a total angular momentum of zero. Since the electrons are identical particles and they are in the same radial state. Before going on to make the total angular momentum states. The symmetry will alternate as we go down in the quantum number. So let’s do the spinor arithmetic. The overall state must be antisymmetic so we can use: = = = 1 s = 1 j = 0. states of deﬁnite total angular momentum will be the energy eigenstates. For low Z atoms.
. the angular momentum part of the wavefunction must be antisymmetric under interchange. s.
1 2
(electrons).7. This will limit the allowed states. Silicon. 1. m. and Germanium. We will (and must) keep track of the intermediate and s quantum numbers. 3 P1 . The s = 1 state is symmetric and the s = 0 state is antisymmetric. The overall symmetry of a state will be a product of the these two symmetries (since when we add and s to give j we are not adding identical things anymore).7.
Normally we will not bother to include that the spins are one half since that’s always true for electrons. we need them to identify the states. So. We need to add four angluar
J = L 1 + L 2 + S1 + S2 We will ﬁnd it useful to do this addition in two steps.
So the total angular momentum quantum number of the initial state is j = 1. Sj ] = [Si
+ Si . Lets operate on this equation with S− . The pion is known to have spin 0. F2. Sj ] + [Si .1
Derivations and Computations
Commutators of Total Spin Operators
S
= S(1) + S(2)
(1) (1)
[Si .8. 1 D2 .
3
Because the neutrons are identical fermions. Pπ = (−1) . π + d → n + n. implying = 0 in the initial state.
20. so = 1 ⇒ Pπ = −1. the allowed states of two neutrons are 1 S0 .2
Using the Lowering Operator to Find Total Spin States
The total spin lowering operator is S− = S− + S− .. and the neutron spin 1 .4 .
20. 3 P0. The pion is captured by the deuteron from a 1S states.2 . So the parity of the initial state is (−1) Pπ Pd = (−1)0 Pπ Pd = Pπ The parity of the ﬁnal state is Pn Pn (−1) = (−1) Therefore. The internal 2 parity of the deuteron is +1.8.E. the deuteron spin 1. Sj ] + [Si . First the RHS gives S − χ+ χ+ = S − χ+
(1) (2) (1) (1)
(1) (2)
χ+ + χ+
(2)
(1)
S − χ+
(2) (2)
= h χ− χ+ + χ+ χ− ¯
(1) (2)
(1) (2)
.8
20.
. S − χ+ = h ¯
(1) (1) (1) (2)
1 2
3 2
−
1 2
−1 (1) (1) ¯ χ− = h χ− 2
Now we want to identify χ11 = χ+ χ+ .1.D. Sj
(1)
(2)
(1)
+ Sj ]
(2) (2) (1) (2) (2) (2) ijk Sk
(2)
= [Si ..3.318 We can determine the internal parity of the pion by studying pion capture by a deuteron. Sj ] = i¯ h
(1) ijk Sk
(1)
+ 0 + 0 + i¯ h
= i¯ h
ijk Sk
Q. The only state with j = 1 is the 3 P1 state. First lets remind ourselves of what the individual lowering operators do. Sj ] + [Si .
−1 . Lowering the LHS. S2 S 2 χ+ χ+
(1) (2) 2
=
S1 + S2
2 2 = S1 + S2 + 2 S1 · S2 (1) (2) (1) (2) (1) (2)
= s1 (s1 + 1)¯ 2 χ+ χ+ + s2 (s2 + 1)¯ 2 χ+ χ+ + 2S1 χ+ · S2 χ+ h h 3 2 (1) (2) (1) (2) (1) (2) (1) (2) (1) (2) χ+ χ+ h ¯ χ+ χ+ + 2 S x S x + S y S y + S z S z = 2
S x χ+ S y χ+ S x χ− S y χ−
= = = =
h ¯ 2 h ¯ 2 h ¯ 2 h ¯ 2
0 1 1 0 0 −i i 0 0 1 1 0 0 −i i 0
1 0 1 0 0 1 0 1
=
h ¯ 2 h ¯ 2
= = h ¯ 2
=
h ¯ 2
h ¯ χ− 2 h ¯ 0 = i χ− i 2 h ¯ 1 = χ+ 0 2 h ¯ −i = −i χ+ 0 2 0 1 =
. h
Therefore we have found 3 s=1 states that work together. 2 Now we can lower this state.319 Operating on the LHS gives S− χ11 = h ¯ So equating the two we have √ (1)(2) − (1)(0)χ10 =
(1) (2)
√ 2¯ χ10 .
2¯ χ10 = h χ− χ+ + χ+ χ− h ¯
(1) (2)
1 (1) (2) (1) (2) χ10 = √ χ− χ+ + χ+ χ− . They are all symmetric under interchange of the two particles. gives √ 1 1 (1) (2) (1) (2) (1) (2) (1) (2) (1) (2) ¯ S− √ χ+ χ− + χ− χ+ = h √ χ− χ− + χ− χ− = 2¯ χ− χ− h 2 2 ⇒ χ1.
20.8.3
Applying the S 2 Operator to χ1m and χ00 . h .
We wish to verify that the states we have deduced are really eigenstates of the S 2 operator.−1 = χ− χ−
(1) (2)
(1)(2) − (0)(−1)χ1(−1) =
√ 2¯ χ1. We will really compute this in the most brute force. We could verify this by using the S 2 operator. There is one state left over which is orthogonal to the three states we identiﬁed. Orthogonal state: 1 (1) (2) (1) (2) χ00 = √ χ+ χ− − χ− χ+ 2 We have guessed that this is an s = 0 state since there is only one state and it has m=0. we get S− χ10 = h ¯ Lowering the RHS.
8. Now lets do the χ00 state. so that the 2¯ is what we expected to get. We will do this by operating with the J 2 operator and setting the coeﬃcients so that we have eigenstates. J 2 ψjmj = j(j + 1)¯ 2 ψjmj h We choose to write the the quantum number mj as m + 1 . This conﬁrms that we have an s=1 h state.320
S 2 χ+ χ+
(1) (2)
= = =
3 2 (1) (2) ¯ 2 h h ¯ χ+ χ+ + 2 2 h 3 2 (1) (2) ¯ h ¯ χ+ χ+ + 2 2
2
0 1 0 1
1
0 1 0 1
+
2
0 i 0 1
1
0 i 0 1
+
2
1 0 1 0
1
1 0 1 0
2
−
2
+
2
1
1
1
2
h 3 2 (1) (2) ¯ 2 (1) (2) (1) (2) h ¯ χ+ χ+ + χ+ χ+ = 2¯ 2 χ+ χ+ h 2 2
Note that s(s + 1) = 2.4
Adding any
plus spin
1 2. ψj(m+ 1 ) = αY m χ+ + βY (m+1) χ− 2 audio
m
and
.) The z component of the total angular momentum is just the sum of the z components from the orbital and the spin. (Other choices would have been possible. S 2 χ00 = = = =
2 2 S1 + S2 + 2S1 · S2 χ00 2 2 (1) (2) (1) (2) (1) (2) S1 + S2 + 2 Sx Sx + Sy Sy + Sz Sz 2 2 (1) (2) (1) (2) (1) (2) S1 + S2 + 2Sz Sz + 2 Sx Sx + Sy Sy
χ00 χ00
3 3 1 + −2 4 4 4
(1) (2) (1) (2) h ¯ 2 χ00 + 2 Sx Sx + Sy Sy χ00
1 (1) (2) (1) (2) √ χ(1) χ(2) − χ(1) χ(2) = h2 χ00 + 2 Sx Sx + Sy Sy ¯ + − − + 2 h ¯2 1 √ χ(1) χ(2) − χ(1) χ(2) + i(−i)χ(1) χ(2) − (−i)iχ(1) χ(2) = h2 χ00 + ¯ − + + − − + + − 2 2 1 (1) (2) (1) (2) (1) (2) (1) (2) = h2 χ00 − √ χ+ χ− − χ− χ+ + χ+ χ− − χ− χ+ ¯ 2 2 h = h2 (1 − 1) χ00 = 0¯ 2 χ00 ¯
20. Y (m+1) . mj = ml + ms There are only two product states which have the right mj = m + 1 . If the spin is up we need Y 2 if the spin is down.
We wish to write the states of total angular momentum j in terms of the product states Y m χ± . This is really just the deﬁntion of the dummy 2 variable m.
h h J 2 ψj. 3 − − 1 = j(j + 1) − ( + 1) − . j(j + 1) − ( + 1) − 3 −m α = 4 ( − m)( + m + 1)β j(j + 1) − ( + 1) − 3 + (m + 1) β 4
( − m)( + m + 1)α =
Now we just cross multiply so we have one equation with a common factor of αβ. we get two equations.m+1 χ−
+ 2(m + 1)
−1 2
Y
. we can solve it if 3 = j(j + 1) − ( + 1) − . giving us two equations. The Y m χ+ term gives αj(j + 1) = α The Y
(m+1) χ−
( + 1) +
3 +m +β 4
( + 1) − m(m + 1).
term gives βj(j + 1) = β ( + 1) + 3 − (m + 1) + α 4 ( + 1) − m(m + 1). if we notice the similarity between the LHS and RHS.m+ 1 = j(j + 1)¯ 2 αYlm χ+ + βY 2 2
.
Collecting α terms on the LHS and β terms on the RHS. So operate on the right hand side with J 2 . 4 If we look a little more carefully at the LHS. 4 These are now simple to solve j(j + 1) = ( + 1) + + 3 ⇒ 4 j= + 1 2
. J 2 ψj. ( − m)( + m + 1) = j(j + 1) − ( + 1) − 3 −m 4 j(j + 1) − ( + 1) − 3 + (m + 1) 4
While this equation looks like a mess to solve.(m+1) χ−
Since the two terms are orthogonal.m+ 1 = j(j + 1)¯ 2 ψj.m+1 χ−
+
β¯ 2 h +
3 + Y 4
.m+1 χ−
( + 1) − (m + 1)m
(1)Ylm χ+
And operate on the left hand side.m+ 1 = 2 α h ¯2 3 1 ( + 1)Ylm χ+ + Ylm χ+ + 2m Ylm χ+ 4 2 √ + ( + 1) − m(m + 1) 1Yl(m+1) χ− ( + 1)Y
. we can see that another solution (which just interchanges the two terms in parentheses) is to replace by − − 1. we can equate the coeﬃcients for each term.321 We will ﬁnd the coeﬃcients α and β so that ψ will be an eigenstate of J 2 = (L + S)2 = L2 + S 2 + 2Lz Sz + L+ S− + L− S+ .
audio + + 1 2 1 2 1 2 m+ 1 2 1 2 m 11 22 = = = = α= β= 0 0 +m+1 2 +1 −m 2 +1
1 1 −1 (m + 1) 2 2 2 1 1 1 1 −1 + m+ m 2 2 2 2 2 1 1 1 11 m+ + (m + 1) 2 2 2 22 m+
Similarly − − 1 2 1 2 1 2 m+ 1 2 1 2 1 2 m 11 22 = = − −m 2 +1 +m+1 2 +1
m+
(m + 1)
1 −1 2 2
. ( − m)2 ( − m) α2 = α2 β2 = ( − m)( + m + 1) ( + m + 1) α2 + β 2 = 1 ⇒ α= −m +m+1 +m+1+ −m 2 α =1 +m+1 +m+1 2 +1 +m+1 = 2 +1 −m 2 +1
β=
So we have completed the calculation of the coeﬃcients. We will make use of these in the hydrogen atom. Writing this in the notation of matrix elements or ClebschGordan coeﬃcients of the form. Plugging j = +
1 2
into our ﬁrst equation. We will normalize the wave function by setting α2 + β 2 = 1. ( − m)α = ( − m)( + m + 1)β
we get the ratio between β and α. jmj s m sms we get. particularly for the anomalous Zeeman eﬀect. We now need to go ahead and ﬁnd α and β. So lets get the squares.322 3 ⇒ 4 1 2
j(j + 1) = ( + 1) − − 1 +
j= −
So these are (again) the two possible values for j.
) Show by direct calculation that. (l = 0. Find the eigenvalues ¯ h ¯ and eigenfunctions of the system of two particles (a) when both particles have spin 1 .
1+ 2
2
2
2
2
(2 + 1) =
=
1− 2
(2(
n=0
1
−
2
+ n) + 1) = (2
2
+ 1)(2
1
−2
2
+ 1) + 2
n=0
n
= (2 This is what we expect. Find the allowed total spin states of two spin 1 particles. What are the possible quantum numbers j and f for an atom in the ground state? What are the possible quantum numbers for an atom in the 2p state?
. and the orbital angular momentum. 7. for the triplet spin states of two spin 1 particles. Lets add up the number of states of total . 2. φ? What is it for spin down? What is the probability density independent of spin? (Do not leave your answer in terms of spherical harmonics. Deﬁne J = L + S in the usual way and F = J + I where I denotes the nuclear spin operator. With a neutral atom.323 20. Find the 3 3 possible values and the probabilities of the z component of the electron’s total angular momentum. 4. φ)χ+ + 2 Y11 (θ.. Show that for the 2 singlet state σ1 · σ2 χ00 = −3χ00 . The n = 2 states of hydrogen have an 8fold degeneracy due to the various l and m states allowed and the two spin states of the electron. we have three angular momenta to add. What are the possible spin and total angular momentum states of two deuterons. Show that the orbital angular momentum of their relative motion can only be even.
If we add 1 to 2 there are (2 1 + 1)(2 2 + 1) product states. . σ1 · σ2 χ1m = χ1m for all allowed m. What happens in (a) when the two particles are 2 identical?
3. The state of an electron is given by ψ = R(r)[ 1 Y10 (θ.. Consider a system of two spinless identical particles. The spin orbit interaction partially breaks the degeneracy Ae2 by adding a term to the Hamiltonian H1 = 2m2 c2 r3 L · S. Ylm . To keep things simple we assume we ordered things so 1 ≥ 2 .8.
2
+ 1)(2
1
−2
2
+ 1) + (2
2
+ 1)(2 2 ) = (2
2
+ 1)(2
1
+ 1)
20. 5.9
Homework Problems
1. The nucleus of a deuterium (A=2 isotope of H) atom is found to have spin 1.) 6. The Hamiltonian of a spin system is given by H = A + B S12·S2 + C(S1zh 2z ) . φ)χ− ]. the electron spin. θ. (b) when 2 one particle has spin 1 and the other spin 1. the nuclear spin. Do the same for the total angular momentum squared. A deuteron has spin 1.5 Counting the States for  −
2
1
≤j≤
1
+
2. Explicitly write out the 9 states which are eigenfunctions of S 2 and Sz . Include orbital angular momentum and assume the two particles are identical. and χ± .
+S 2. What is the probability density for ﬁnding an electron with spin up at r. 4. Use ﬁrst order perturbation theory to ﬁnd how the degeneracy is broken under the full Hamiltonian and write the approximate energy eigenstates in terms of Rnl .
A hydrogen atom is in the state ψ = R32 Y21 χ− . and for l = 0? List all the allowed states giving. what are the possible outcomes of this measurement and what are the probabilities for each outcome? If a measurement of the energy of the state is made. (S = S1 + S2 ) (a) What are the allowed values of s. and  − − . 2 a) What are the allowed states of total spin for l = 0 and for l = 1? b) List the allowed states using spectroscopic notation for l = 0 and 1. for l = 1. j. (c) Now apply the lowering operator to get the other ms states. Two identical spin 3 particles are bound together into a state with orbital angular momentum l. χ+ . We want to ﬁnd the eigenstates of total S 2 and Sz for two spin 1 particles which have an S1 · S2 interaction.  − + . 4 h 1 Jz ψ = − 2 ¯ ψ. the total spin quantum number. Use sms notation and s1 m1 s2 m2 for the product states. Two diﬀerent spin 1 particles have a Hamiltonian given by H = E0 + h2 S1 · S2 + B (S1z + S2z ). what is the probability to measure J 2 = 12¯ 2 ?
. 7. 2 h ¯ ¯ Find the allowed energies and the energy eigenstates in terms of the four basis states  + + . χ0 . in terms of the ml .  + − . what are the possible energies and the probabilities of each? You may ignore the nuclear spin in this problem. for each state. You only need to go down to ms = 0 because of the obvious symmetry. L2 . Two (identical) electrons are bound in a Helium atom.
A 9. Write out the j. (That is give one state for every mj value. χ− . χ0 .) If the particle is prepared in the state h ml = 0. What are the possible outcomes of this combined measurement and what are the probabilities of each? You may ignore nuclear spin in this problem. ms = 0 . If a measurement of J 2 and of Jz is made. ms basis. Determine the quantum numbers of this h 2 state as well as you can. what are the possible outcomes and what are the probabilities of each. L2 ψ = 6¯ 2 ψ. What are the allowed states of total spin (s) for l = 2. Two identical spin 1 particles are bound together into a state with orbital angular momentum l. Find the allowed values of the total angular momentum quantum number. (d) Now ﬁnd the states with the other values of s in a similar way. (b) Write down the states of maximum ms for the maximum s state. A spin 1 particle is in an = 2 state. You need not list all the diﬀerent mj values.10
Sample Test Problems
1. A hydrogen atom is in the state ψ = R43 Y30 χ+ . What values are allowed for each of these states? Explicitly write down the (2s + 1) states for (1) (2) (1) (2) (1) (2) the highest s in terms of χ+ . What are the allowed states jlsl1 l2 if both electrons have principal quantum number n = 1? What are the states if one has n = 1 and the other n = 2? h 5. and of Jz such that J 2 ψ = 15 ¯ 2 ψ.
10. 6. A combined measurement of of J 2 and of Jz is made. 4. 8. the values of the quantum numbers for total angular momentum (j). mj states for the largest allowed j value. If a measurement of Lz is made.324
20. (2s+1 Lj ) 2. and of course the electron’s spin is 1 . 3. A hydrogen atom is in an eigenstate (ψ) of J 2 . orbital angular momentum (l) and spin angular momentum (s) if l is 2 or less. and χ− . List all the allowed states of total spin and total zcomponent of spin for 2 identical spin 1 particles.
A measurement of J 2 . ψj. What are the possible outcomes and what are the probabilities of each outcome? You may ignore nuclear spin in this problem.mj = ψ ψj. Two diﬀerent spin 1 particles have a Hamiltonian given by H = E0 + AS1 · S2 + B(S1z + S2z ).m+1 χ−
. 12.m+ 1 2 2 − 1 .m+ 1 2 = 2−m = 2(3)+1 = 2 . and χ− χ− . The two possible values of the total 2 angular momentum quantum number are j = ± 1 = 5 . the total angular momentum squared.m+ 1 2 = +m+1 = 2(3)+1 = 5 . +1 7 2 2 2
79 2 h 2 2¯
is simply is simply
57 2 h 2 2¯
.m+ 1 2 2
= =
+m+1 −m Y m χ+ + Y 2 +1 2 +1 −m +m+1 Y m χ+ − Y 2 +1 2 +1
. 7 . 2 +1 7 2 2 2 The probability to be in the second state which has a measured value of J 2 of 3−1 P 5 =  Y31 χ+ ψ − 1 . χ− χ+ . 2 (1) (2) Find the allowed energies and the energy eigenstates in terms of the four product states χ+ χ+ . is made. These total angular momentum 2 2 2 states are given in the formulas and its easily seen that the m = 1 version of the formula should be used.325 11. A hydrogen atom is in the state ψ = R43 Y31 χ+ . The atom is in a state with = 3 added to a spin 1 electron. (1) (2) (1) (2) (1) (2) χ+ χ− .mj = ψ
+ 1 .m+1 χ−
The probability to be in the ﬁrst state which has a measured value of J 2 of 3+1+1 P 7 =  Y31 χ+ ψ + 1 .
we compute the coro rections to the energies and eigenfunctions. Cases in which the Hamiltonian is time dependent will be handled later. and second order terms in the series. To solve it using a perturbation series.
21. En ψn cnk = = =
(0) (1) (2) En + En + En + . Chapter XI. If the eigenstates are (nearly) degenerate to zeroth order. in CohenTannoudji et al. (1). ⎞ ⎛
N ⎝φn +
k=n (1) cnk
cnk φk ⎠ + ..4. cannot be solved exactly. we will expand both our energy eigenvalues and eigenstates in powers of the small perturbation. like the harmonic oscillator and the hydrogen atom. First order perturbation theory will give quite accurate answers if the energy shifts calculated are (nonzero and) much smaller than the zeroth order energy diﬀerences between eigenstates.326
21
Time Independent Perturbation Theory
Perturbation Theory is developed to deal with small corrections to problems which we have solved exactly. ﬁrst. we will diagonalize the full Hamiltonian using only the (nearly) degenerate states.
+
(2) cnk
where the superscript (0). If the ﬁrst order correction is zero.1)
(1) En
=
φn H1 φn
. like most problems. By solving the Schr¨dinger equation at each order of the perturbation series. N is there to keep the wave function normalized but will not play an important role in our results. and in Griﬃths Chapters 6 and 7. We will make a series expansion of the energies and eigenstates for cases where there is only a small correction to the exactly soluble problem.. we will go to second order. (see section 21... H = H0 + H 1 The Schr¨dinger equation for the full problem is o (H0 + H1 )ψn = En ψn Presumably this full problem. (2) are the zeroth. This material is covered in Gasiorowicz Chapter 16.1
The Perturbation Series
Assume that the energy eigenvalue problem for the Hamiltonian H0 can be solved exactly
(0) H0 φn = En φn
but that the true Hamiltonian has a small additional term or perturbation H1 .
the zeroth order state will be allowed to be an arbitrary linear combination of the degenerate states and the eigenvalue problem will be solved. En . The second order correction to the (2) energy. By looking at the zeroth and ﬁrst order terms in the Schr¨dinger equation and dotting it into one of o the degenerate states φ(j) .327 φk H1 φn En − Ek
(0) k=n (0) (0)
cnk
(1)
= =
(2) En
 φk H1 φn 2 En − Ek
(0)
audio So the ﬁrst order correction to the energy of the nth eigenstate.2
Degenerate State Perturbation Theory
The perturbation expansion has a problem for states very close in energy. The series does not converge. the Stark Eﬀect. with anharmonic perturbation (ax4 ).2) the energy equation for ﬁrst order (nearly) degenerate state perturbation theory φ(j) H0 + H1 φ(i) αi = Eαj . Then we will need to use the second order (2) term En to estimate the correction. depends on a matrix element and the energy diﬀerence between states.2: Hydrogen Atom in a Eﬁeld. The energy diﬀerence in the denominators goes to zero and the corrections are no longer small. Assume that two or more states are (nearly) degenerate. That is. The actual calculation of the matrix elements depends greatly on the problem being solved.*
(1)
Sometimes the ﬁrst order correction to the energy is zero.O. The application of the ﬁrst order perturbation equations is quite simple in principal.3. and other eﬀects in Hydrogen. cnk . * See Example 21. En . * See Example 21. We can very eﬀectively solve this problem by treating all the (nearly) degenerate states like we did φn in the regular perturbation expansion. We will use the indices i and j to label the states in N . is just the expectation (1) value of the perturbation in the unperturbed state. we derive (see section 21. Deﬁne N to be the set of those nearly degenerate states. has a similar dependence.*
We will exercise the use of perturbation theory in section 22 when we compute the ﬁne structure.1: H. Note that the higher order corrections may not be small if states are nearby in energy. This is true when we apply an electric ﬁeld to a hydrogen atom.3.
i∈N
.
21. The ﬁrst order admixture of φk in ψn .4. Choose a set of basis state in N which are orthonormal φ(j) φ(i) = δji where i and j are in the set N .
.3: The Stark Eﬀect for n=2 States. Hn2 ⎞⎛ ⎞ ⎛ ⎞ α1 α1 . E2 .3.. φ21(−1) and 1 √ (φ200 ± φ210 ) with energies of E2 . Hnn
where Hji = φ(j) H0 + H1 φ(i) is the matrix element of the full Hamiltonian. * See Example 21.. H1n ... and φ21(−1) .. Hn1 H12 H22 .. H2n ⎟ ⎜ α2 ⎟ ⎜ α2 ⎟ ⎠⎝ ⎠=E⎝ ⎠ . The degenerate states φ200 .1
Examples
H. If there are n nearly degenerate states.. αn αn ...*
The perturbation due to an electric ﬁeld in the z direction is H1 = +eEz. That is H0 φ2 m = E0 φ2 m . there are n solutions to this equation. Written as a matrix..O.. First. φ211 . .
We add an anharmonic perturbation to the Harmonic Oscillator problem.. H1 = ax4 Since this is a symmetric perturbation we expect that it will give a nonzero result in ﬁrst order perturbation theory.3
21... audio We recognize this as simply the (matrix) energy eigenvalue equation limited the list of degenerate states. with anharmonic perturbation (ax4 ). The Stark eﬀect for the (principle quantum number) n=2 states of hydrogen requires the use of degenerate state perturbation theory since there are four states with (nearly) the same energies. . φ210 . write x in terms of A and A† and compute the expectation value as we have done before. . correct to ﬁrst order. We solve the equation to get the energy eigenvalues and energy eigenstates. 2
21.
(1) ΔEn
= = = =
a nx4 n =
a¯ 2 h n(A + A† )4 n 4m2 ω 2
a¯ 2 h n(AAA† A† + AA† AA† + AA† A† A + A† AAA† + A† AA† A + A† A† AA)n 4m2 ω 2 a¯ 2 h (n + 1)(n + 2) + (n + 1)2 + n(n + 1) + n(n + 1) + n2 + n(n − 1) 4m2 ω 2 3a¯ 2 h (2n2 + 2n + 1) 4m2 ω 2
. The linear combinations that are found to diagonalize the full Hamiltonian in the subspace of degenerate states are: φ211 .. For our ﬁrst calculation.328 This is an eigenvalue equation with as many solutions as there are degnerate states in our set...3. the equation is ⎛ H11 ⎜ H21 ⎝ . we will ignore the hydrogen ﬁne structure and assume that the four states are exactly degenerate. and E2 ∓ 3eEa0 . each with unperturbed energy of E0 .
We choose the axes so that the Electric ﬁeld is in the z direction.2 Hydrogen Atom Ground State in a Eﬁeld. 1 Y00 cos θ = √ 4π 4π Y10 3
(1)
The we can just use the orthonormality of the spherical harmonics to do the angular integral. E100
(2) ∞
and m. ∗ ∗ φnlm zφ100 = d3 rRnl (r cos θ)R10 Ylm Y00 We can do the angular integral by converting the cos θ term into a spherical harmonic.329 21. the ﬁrst order correction to the energy is zero because the expectation value of z is an odd function.
We have solved the Hydrogen problem with the following Hamiltonian. For nondegenerate states. This involves a sum over all the other states. H1 = eEz It is typically a small perturbation. yielding. The perturbtion is then.  φnlm zφ100  =
2
1 28 n7 (n − 1) 3 (n + 1)2n+5
2n−5
a2 δ 0 δm0 ≡ f (n)a2 δ 0 δm0 0 0
We put this back into the sum. the Stark Eﬀect. The Kronecker deltas eliminate the sums over energy denominators in terms of the Bohr radius. 2  φnlm zφ100  (2) E100 = e2 E 2 (0) (0) E1 − En nlm=100 We need to compute all the matrix elements of z between the ground state and the other Hydrogen states. We write the
=
e2 E 2
−e2 n=2 2a0
f (n)a2 0 2 + 2ae n2 0
. Enlm = eE φnlm zφnlm = 0 We therefore need to calculate the second order correction. φnlm zφ100 = = 1 ∗ ∗ √ r3 drRnl R10 dΩYlm Y10 3 δ 1 δm0 ∗ √ r3 Rnl R10 dr 3
The radial part of the integral can be done with some work. H0 = Ze2 p2 − 2μ r
Now we want to ﬁnd the correction to that solution if an Electric ﬁeld is applied to the atom.3. leaving us with a radial integral to do.
Because of the exact degeneracy (H0 φ(j) = E0 φ(j) ). φ211 . we will ignore the hydrogen ﬁne structure and assume that the four states are exactly degenerate. There are 4 eigenvalues (E0 + E (1) ).25a3E 2 0 0 The ﬁrst two terms of the sum get us pretty close to the right answer.
i
This is esentially a 4X4 matrix eigenvalue equation. . We could have just done those radial integrals. distinguished by the index n.
21. d=− ∂ΔE = 4(1. Now we compute d. This indicates why the energy shift is second order. each with unperturbed energy of E0 .
The Stark eﬀect for the n=2 states of hydrogen requires the use of degenerate state perturbation theory since there are four states with (nearly) the same energies. H0 and E0 can be eliminated from the equation. and φ21(−1) .74 + 0. That is H0 φ2 m = E0 φ2 m . The perturbation due to an electric ﬁeld in the z direction is H1 = +eEz. For our ﬁrst calculation.) = −2. In fact.10 + . E100 = −2a3 E 2 (0. . So our ﬁrst order degenerate state perturbation theory equation is αi φ(j) H0 + eEz φ(i) = (E0 + E (1) )αj .3
The Stark Eﬀect for n=2 Hydrogen. φ210 . indicating that it is induced. αi (E0 δij + φ(j) eEz φ(i) )
i
= (E0 + E (1) )αj = E0 αj + E (1) αj = E (1) αj
E0 αj +
i
αi φ(j) eEz φ(i) αi φ(j) eEz φ(i)
i
. the electric dipole moment of the atom which is induced by the electric ﬁeld. we could just start with the ﬁrst few states to get a good idea of the size of the eﬀect. The E ﬁeld induces the dipole moment. The result comes out to be. then the dipole moment interacts with the E ﬁeld causing a energy shift.125)a3E 0 ∂E
(2)
The dipole moment is proportional to the Electric ﬁeld.330
∞
= =
a3 E 2 0
2f (n) 1 −1 + n2 n=2 n2 f (n) n2 − 1 n=2
∞
−2a3 E 2 0
This is all a little dissatisfying because we had to insert the general formula for the radial integral and it just goes into a nasty sum.3. The degenerate states φ200 .
like the hydrogen ﬁne structure. as we would expect in ﬁrst order (degenerate) perturbation theory. and with eigenvalues (of H1 ) of 0. Another way of saying this is that the operator z doesn’t “change” m. 1 √ 3 r a0 e−r/2a0 Y10 d3 r
2 1−
r 2a0
e−r/2a0 Y00 z (2a0 )
−3/2
r 1 r 2eE (2a0 )−3 √ r3 d3 r 1 − e−r/a0 2a0 a0 3 ∞ r4 1 1 r5 2eE(2)−3 √ √ − 5 e−r/a0 dr a4 2a0 3 3 0 0 ∞ ∞ 1 a0 eE x4 e−x dx − x5 e−x dx 12 2 0 0 a0 eE 5·4·3·2·1 4·3·2·1− 12 2 a0 eE (−36) 12 −3eEa0 ⇒ E (1) = ∓3eEa0
1 √ cos θY10 dΩ 4π
This is ﬁrst order in the electric ﬁeld. φ21−1 . Recall Y00 = γ = = = = = = = eE (2a0 )
−3/2 √1 4π
(φ200 ± φ210 )
and Y10 =
3 4π
cos θ. z] = 0.331 This is just the eigenvalue equation for H1 which we can write out in (pseudo)matrix form ⎛ ⎞ ⎛ ⎞ ⎛ α1 ⎞ α1 ⎜ α2 ⎟ (1) ⎜ α2 ⎟ ⎝ H1 ⎠ ⎝ ⎠ = E ⎝ ⎠ α3 α3 α4 α4 Now. Here is a little proof. ⎛ ⎞ ⎞⎛ ⎞ γ 0 α1 α1 0 0 ⎟ ⎜ α2 ⎟ ⎜ α2 ⎟ (1) ⎠⎝ ⎠ = E ⎝ ⎠ α3 α3 0 0 α4 α4 0 0
1 √ 2
We can see by inspection that the eigenfunctions of this operator are φ211 . If the states are not exactly degenerate. What remains is to compute γ. Ylm [Lz . most of the matrix elements of H1 are zero. Lets deﬁne the one remaining nonzero (real) matrix element to be γ. γ = eE φ200 z φ210 The equation (labeled with the basis states ⎛ φ200 0 0 φ211 ⎜ 0 0 ⎝ φ210 γ 0 φ21−1 0 0 to deﬁne the order) is. in fact. we have to leave in the diagonal terms of H0 . where Δ comes from some other perturbation. 0.) γ E0 − Δ γ E0 + Δ α1 α2 =E α1 α2
. Assume that the energies of the two (mixed) states are E0 ± Δ. and ±γ. z] Yl m = 0 = (m − m ) Ylm z Yl m This implies that Ylm z Yl m = 0 unless m = m . (The φ211 and φ21(−1) are still not mixed by the electric ﬁeld. We will show that because [Lz . that all the matrix elements between states of unequal m are zero.
we will expand both our energy eigenvalues and eigenstates in powers of λ. En ψn cnk (λ) = = =
(0) (1) (2) En + λEn + λ2 En + .4
21. The ﬁrst order equation dotted into φn yields
(1) φn λH1 φn = λEn
..
The full Schr¨dinger equation is o ⎞ ⎛ (H0 + λH1 ) ⎝φn +
k=n
⎛
k=n
⎞ cnk (λ)φk ⎠
(0) (1) (2) cnk (λ)φk ⎠ = (En + λEn + λ2 En + . It is there to do the bookkeeping correctly and can go away at the end of the derivations. Δ same order. λ0 λ1 λ2 H0 φn = En φn λH1 φn + H0 λ
k=n (0)
cnk φk = λEn φn + λEn
k=n
(1)
(1)
(0)
H0
k=n
λ2 cnk φk + λH1
(2)
λcnk φk = En
(1)
(0)
k=n (2) λ2 cnk φk k=n
cnk φk + λEn
(1) k=n
(1)
λcnk φk + λ2 En φn
(1)
(2)
The zero order term is just the solution to the unperturbed problem so there is no new information there. and γ
γ 2 + Δ2
Δ. γ. It is also correct when the two corrections are of the
21. This means we can dot the equations into each of the φi to get information. To solve the problem using a perturbation series.4. For this equation to hold as we vary λ. ⎞ ⎛
N (λ) ⎝φn +
k=n (1) (2)
cnk (λ)φk ⎠
λcnk + λ2 cnk + .332 E = E0 ± This is OK in both limits.. much like getting the components of a vector individually.1
Derivations and Computations
Derivation of 1st and 2nd Order Perturbation Equations
To keep track of powers of the perturbation in this derivation we will make the substitution H1 → λH1 where λ is assumed to be a small parameter in which we are making the series expansion of our energy eigenvalues and eigenstates.. We will investigate the ﬁrst three terms. we will dot the equation into φn and separately into all the other functions φk .) ⎝φn +
where the N (λ) has been factored out on both sides.... it must hold for each power of λ. Since φn is treated separately in this analysis. The other two terms contain linear combinations of the orthonormal functions φi .
Solving for the second order correction to the energy (1) and substituting for cnk . These results are rewritten with all the λ removed in section 21. we have
(2) λ2 En = k=n
 φk λH1 φn 2 En − Ek
(0) (0)
.
k=n (1) (2)
We will not need the projection on φk but could proceed with it to get the second order correction to the wave function.
1 N (λ)2
= φn +
k=n
λcnk φk φn + N (λ) ≈ 1 −
1 2
(1)
k=n
λcnk φk = 1 + λ
2 (1) cnk 2
(1)
k=n
λ2 cnk 2
(1)
k=n
The correction is of order λ2 and can be neglected at this level of approximation.
21. In the following equation. We do need to go back and check whether the ﬁrst order corrected wavefunction needs normalization. we will allow an arbitrary linear combination of those states at zeroth order. ⎛ ⎞ ψn = N (λ) ⎝
i∈N
αi φ(i) +
k∈N
(1) λcnk φk + . We will only go to ﬁrst order in this derivation and we will use λ as in the previous derivation to keep track of the order in the perturbation. (0) (1) (1)
From these it is simple to derive the ﬁrst order corrections
(1) λEn = φn λH1 φn φk λH1 φn (1) λcnk = (0) (0) En − Ek
The second order equation projected on φn yields λcnk φn λH1 φk = λ2 EN .1.4. if that were needed.
.. the sum over i is the sum over all the states degenerate with φn and the sum over k runs over all the other states.2
Derivation of 1st Order Degenerate Perturbation Equations
To deal with the problem of degenerate states.⎠
where N is the set of zeroth order states which are (nearly) degenerate with φn .333 and dotted into φk yields
(0) φk λH1 φn + Ek λcnk = En λcnk ..
The normalization factor N (λ) played no role in the solutions to the Schr¨dinger equation since o that equation is independent of normalization.
3.
. Now solve the problem exactly. Find the lowest order nonzero shifts in the energies of the ground state and the ﬁrst excited state if a constant ﬁeld E1 is applied. our calculation gives us the full energy to ﬁrst order. Assume p = m dx and write dt terms of the commutator [H. If the general form of the spinorbit coupling for a particle of mass m and spin S moving in a potential V (r) is HSO = 2m1 c2 L · S 1 dV (r) . Calculate the eﬀect for the n = 2 states. 4.. a good approximation to its charge distribution is a uniform charge density over a sphere of radius 0. not just the correction. o ⎛ (H0 + λH1 ) ⎝
i∈N
⎞
⎛ αi φ(i) +
i∈N k∈N
⎞ cnk (λ)φk ⎠
αi φ(i) +
k∈N
(0) cnk (λ)φk ⎠ = (En + λE (1) + . It has a complicated structure. An electron is bound in a harmonic oscillator potential V0 = 1 mω 2 x2 .5
Homework Problems
1. Consider a two dimensional harmonic oscillator problem described by the Hamiltonian H0 = + 1 mω 2 (x2 + y 2 ). we have (H0 + λH1 )
i∈N
αi φ(i) + H0
k∈N
(0) λcnk φk = (En + λE (1) ) i∈N
(1)
(0) αi φ(i) + En k∈N
λcnk φk .
i∈N
This is just the standard eigenvalue problem for the full Hamiltonian in the subspace of (nearly) degenerate states. Find the same shifts if a ﬁeld E1 x3 is applied. Small electric ﬁelds in the 2 x direction are applied to the system. if the additional potential V = 2λxy is applied.
(1)
Projecting this onto one of the degenerate states φ(j) . but.334 The full Schr¨dinger equation is. we get
(0) φ(j) H0 + λH1 φ(i) αi = (En + λE (1) )αj . i∈N
By putting both terms together. 5. A small additional potential V1 = λ cos( πx ) 2b is applied. A particle is in a box from −a to a in one dimension..5 fermis.
21.
in
6. The result may be simpliﬁed to φ(j) Hφ(i) αi = Eαj . The proton in the hydrogen nucleus is not really a point particle like the electron is. what is the eﬀect of that coupling on the spectrum of 2 r dr a three dimensional harmonic oscillator? Compute the relativistic correction for the ground state of the three dimensional harmonic oscillator. Compare the exact result for the ground state to that from second order perturbation theory.) ⎝
If we keep the zeroth and ﬁrst order terms. It is useful both for degenerate states and for nearly degenerate states. x] to get the result. 2. to ﬁrst order. Calculate the eﬀect of this potential change for the energy of the ground state of hydrogen. Prove that
n p2 +p2 x y 2m
(En − Ea ) nxa 2 =
h2 ¯ 2m
by starting from the expectation value of the commutator
dx dt
[p. Calculate the energies of the ﬁrst and second excited states in this new potential. x] in the state a and summing over all energy eigenstates. Calculate the energy shifts of the ground state and the degenerate 2 ﬁrst excited states.
Calculate the shifts in energy due to the Eﬁeld and give the states that have those energies. Calculate the lowest order nonzero correction to the ground state energy. since spin plays no role here there are just 4 degenerate states. Calculate the energy shifts to all the energy eigenstates in an electric ﬁeld E (in the x direction). A small electric 2 ﬁeld. z] = 0. Ignore the ﬁne structure corrections to the energy since the Eﬁeld is strong. An electron is in a three dimensional harmonic oscillator potential V (r) = 1 mω 2 r2 . (Note. of strength Ez . don’t bother to evaluate the radial integrals. Please work out the problem in principle before attempting any integrals.) 3. 4. Under these assumptions. Remember to use the fact that [Lz . Assume that the 2s and 2p states of Hydrogen are degenerate and spin is not important. there are 4 states: the 2s and three 2p states.335
21.6
Sample Test Problems
1. Find the energies of the n = 2 hydrogen states in a strong uniform electric ﬁeld in the zdirection. is applied in the z direction.
. If you are pressed for time. Hydrogen atoms in the n = 2 state are put in a strong Electric ﬁeld. Assume an electron is bound to a heavy positive particle with a harmonic potential V (x) = 1 2 2 2 mω x . 2.
and in Griﬃths 6. By calculating (see section 22. we will add several corrections: 1. The “Darwin Term” correction to s states from Dirac eq. 4. because it was hard to understand at the time it was ﬁrst measured.1) the next order relativistic correction to the kinetic energy we ﬁnd the additional term in the Hamiltonian H1 = − 1 p4 e .4. in CohenTannoudji et al. 2. This material is covered in Gasiorowicz Chapter 17. It will not be anomalous for us. Correction (1) comes from relativity. Nevertheless. We can estimate the size of this correction compared to the Hydrogen binding energy by taking the p2 ratio to the Hydrogen kinetic energy. 2m = −E =
1 2 2 2 α mc . We will use many of the tools of the last three sections to make our calculations.1
Hydrogen Fine Structure
The basic hydrogen problem we have solved has the following Hamiltonian. 8 m 3 c2
Our energy eigenstates are not eigenfunctions of this operator so we will have to treat it as a perturbation. 3. The electron’s velocity in hydrogen is of order αc.)
p4 p2 p2 (p2 /2m) 1 = ÷ = = α2 3 c2 2 c2 2 8m 2m 4m 2mc 4
.3 and 6. Since the Hydrogen problem still has spherical symmetry. The eﬀect of a weak magnetic ﬁeld is known as the anomalous Zeeman eﬀect. (Remember that. a few of the correction terms we use will not be fully derived here. H0 = Ze2 p2 − 2μ r
To this simple Coulomb problem. We will break the spherical symmetry by applying a weak magnetic ﬁeld. further breaking the degeneracy of the energy eigenstates. The SpinOrbit correction. Some of the degeneracy will be broken.
22. The ((anomalouus) Zeeman) eﬀect of an external magnetic ﬁeld. The relativistic correction to the electron’s kinetic energy.4. we will calculate the ﬁne structure corrections to the Hydrogen spectrum. in the hydrogen ground state. states of deﬁnite total angular momentum will be the energy eigenstates. Chapter XII.336
22
Fine Structure in Hydrogen
In this section. It is not very relativistic but a small correction is in order.
is harder to derive correctly. this is down by a factor of order α2 from the Hydrogen binding energy. The ﬁrst order perturbation energy shift from the spin orbit correction is calculated (see section 22. We will need to use the ψnjmj s to add in the spinorbit. H2 = −μe · B We can derive (see section 22. H2 = 1 ge2 L·S 2 2m2 c2 r3
This will be of the same order as the relativistic correction. due to SpinOrbit interactions. but not on m or j.337 Like all the ﬁne structure corrections. the L · S term should give 0 for = 0! In the above calculation there is an factor which makes the result for = 0 undeﬁned.3) the relativity correction in ﬁrst order perturbation theory . 2 ⎡ (0) 2 4n En ⎣ (0) 3− = En + + 2 2mc +1 2
(0) 2 2n (+)
⎤ ⎦
Enjmj
(
s
−
+ 1 )( 2
+1) 2n ( +1) 2
(−)
Enjmj
s
(0) = En +
En n 3− 2mc2 ( + 1) 2
2 4 − +1 4+ 2
(+) (−)
.4) for the states of deﬁnite j.5) which is important for = 0 and surprisingly makes the above calculation right.2) B from a Lorentz transformation of the E ﬁeld of a static proton (We must also add in the Thomas Precession which we will not try to understand here). ψnlm H2  ψnlm = g = 2 h ge2 ¯ 2 1 [j(j + 1) − ( + 1) − s(s + 1)] 2 c2 2 4m En 2 2mc2
(0) 2 n ( + 1 )( +1) 2 −n ( +1) 2
1 r3
nlm
j= + j= −
1 2 1 2
Actually. Now we compute (see section 22. This means that we could use either the ψnjmj s or the ψn m sms to calculate the eﬀect of H1 . There is an additional Dirac Equation contribution called the “Darwin term” (see section 22.4. even for = 0! We will now add these three ﬁne structure corrections together for states of deﬁnite j.4. We understand the basis for this term. We start with a formula which has slightly diﬀerent forms for j = ± 1 .4.4. ψnlm H1  ψnlm En 4n =+ 3− 2 2mc +1 2
(0) 2
The result depends on and n. The second term. The magnetic moment from the electron’s spin interacts with the B ﬁeld produced by the current seen in the electron’s rest frame from the circulating proton.
338 4 ∓ j+ 1 En 2 3−n 2 2mc +1 2
(0) 2 2
Enjmj
s
(0) = En +
We can write ( + 1 ) as (j + 2 4∓
1 2
∓ 1 ).
Enlm = En +
(0)
(0) En 2mc2
2
3−
4n j+ 1 2
This is independent of so the states of diﬀerent total angular momentum split in energy but there is still a good deal of degeneracy. There are. the states of deﬁnite total angular momentum are the energy eigenstates until we somehow break spherical symmetry. other. causes states of diﬀerent to shift apart slightly. of course. Nevertheless. smaller corrections to the energies. A correction from ﬁeld theory.
.
n=2 P3/2 P3/2 P1/2 S 1/2 P1/2
add Bfield add Darwin + spinorbit
S 1/2
add relativity
We have calculated the ﬁne structure eﬀects in Hydrogen. the Lamb Shift. so that 2 = (j + 1 ∓ 1 ) 4j + 2 ∓ 2 2 2 1 1 1 =4 (j + 2 )(j + 2 ∓ 2 ) (j + 1 ∓ 1 )(j + 1 ) 2 2 2
2 j+ 1 2 +1 2
and we get a nice cancellation giving us a simple formula.
. due to a weak magnetic ﬁeld. and
H3 =
eB eB · (L + 2S) = (Lz + 2Sz ) 2mc 2mc
is the term due to the weak magnetic ﬁeld. A direct calculation (see section 22. which we should add to the ﬁne structure energies. we can do perturbation theory using the states of deﬁnite j.4. the the degeneracy is completely broken for the states ψnjmj s . where H0 = 2μ − Ze is the normal r Hydrogen problem.
ΔE = ψn
jmj
eB 2mc (Lz
+ 2Sz ) ψn
jmj
=
e¯ B h 2mc mj
1±
1 2 +1
This is the correction. H1 + H2 is the ﬁne structure correction.
Enjmj
s
1 = − α2 mc2 2
1 1 α2 + 3 2 n n j+
1 2
−
3 4n
Thus. Lets assume that the ﬁeld is weak enough that the energy shifts due to it are smaller than the ﬁne structure corrections.339
22. In the weak ﬁeld limit. Our 2 p2 Hamiltonian can now be written as H = H0 + (H1 + H2 ) + H3 .
We now run into a problem because H1 + H2 picks eigenstates of J 2 and Jz while H3 picks eigenstates of Lz and Sz .6) of the Anomalous Zeeman Eﬀect gives the energy shifts in a weak B ﬁeld.2
Hydrogen Atom in a Weak Magnetic Field
One way to break the spherical symmetry is to apply an external B ﬁeld. in a weak ﬁeld. All the states can be detected spectroscopically.
For example. the energies of all these n = 3 states are the same.
=2 =1 =2
m =0 m =0 m =2
ms = 1 2 ms = 1 2 1 ms = − 2
. we can neglect the ﬁne structure entirely.
0 E = En +
eB¯ h (m + 2ms ) 2mc
In this limit. but not . H1 + H2 . We will not calculate this here. the ﬁeld has partially removed the degeneracy in m and ms .340
n=2 P3/2 P3/2 P1/2 S 1/2 P1/2
add Bfield add Darwin + spinorbit
S 1/2
add relativity
The factor 1 ± 2 1 is known as the Lande g Factor because the state splits as if it had this +1 gyromagnetic ratio. If the ﬁeld is very strong. as a correction. In the strong ﬁeld limit we could use states of deﬁnite m and ms and calculate the eﬀects of the ﬁne structure. We know that it is in fact a combination of the orbital and spin g factors in a state of deﬁnite j. Then the calculation is easy.
= 2m2 c2
φ only depends on r ⇒ ∇φ = r dφ = ˆ dr H2 =
r dφ r dr
1 dφ 1 dφ −ge ge S·p×r S·L = 2 c2 2 c2 2m r dr 2m r dr
φ=
e r H2 =
⇒
dφ e =− 2 dr r
1 ge2 L·S 2 2m2 c2 r3
. 8 m 3 c2
H1 = −
22. The B ﬁeld from the proton in the electron’s rest frame is v B = − × E. c Therefore the correction is H2 = ge ge S·v×E S·B = − 2mc 2mc2 ge S · p × ∇φ. We can therefore neglect the small correction to the small correction and use 1 p4 e .4.2
The SpinOrbit Correction
We calculate the classical Hamiltonian for the spinorbit interaction which we will later apply as a perturbation. we ﬁnd p 2 c2 + m 2 c4
1/2
= mc2 +
1 p 2 c2 1 p 4 c4 p2 p4 − + · · · ≈ mc2 + − 2 3 c6 2 mc 8m 2m 8m3 c2
p2 2m
So we have our next order correction term.4.3 22. Notice that
was just the lowest order correction to mc2 .1
Examples Derivations and Computations
The Relativistic Correction
Moving from the nonrelativistic formula for the energy of an electron to the relativistic formula we make the change 1/2 p2 p 2 c2 1/2 = mc2 1 + 2 4 . mc2 + e → p2 c2 + m2 c4 2m m c Taylor expanding the square root around p2 = 0.4
22.341
22.
What about the “reduced mass problem”? The proton is very nonrelativistic so only the electron term is important and the reduced mass is very close to the electron mass.
Recall that 1 2 J − L2 − S 2 2 and we will therefore want to work with states of deﬁnite j. the electron is actually in a rotating system which gives an additional L · S term (not from the B ﬁeld!). H2 ∝ L · S =
22. En 1 r 1 r2 = =
n
=
ψnjmj
s
H1  ψnjmj
s
1 = − 2mc2 = −
+2
− 1 α2 mc2 2 n2
e2 e4 + 2 3 a0 n 2 a0 n ( + 1 ) 2
2 4n 1 E (0) 1 − 4 + 2mc2 n +1 2 (0) 2
En 4n = + 3− 2 2mc +1 2
. It is correct for the EM forces.342 Note that this was just a classical calculation which we will apply to quantum states later. but.4. and s.3
Perturbation Calculation for Relativistic Energy Shift
p4
2
p 1 Rewriting H1 = − 1 m3ec2 as H1 = − 2mc2 2m we calculate the energy shift for a state ψnjmj s . we will need to use these states for the spinorbit interaction
2
ψnjmj
s H1  ψnjmj
s
=
− − −
1 2mc2 1 2mc2
ψnjmj ψnjmj
s
p2 2m H0 +
2
ψnjmj e2 r
2
s
= = =
s
ψnjmj
s
=
1 e2 e4 e2 2 ψnjmj s H0 + H0 + H0 + 2 ψnjmj 2mc2 r r r 2 1 e 2 − En + ψnjmj s H0 ψnjmj s 2 2mc r e2 ψnjmj s + H0 ψnjmj s r e4 + ψnjmj s 2 ψnjmj s r 1 1 1 2 − + e4 En + 2En e2 2 2mc r n r2 nl 1 −e2 − α2 mc2 /n2 = 2 2a0 n2 1 a0 n 2 1 a2 n 3 ( + 1 ) 0 2
1 − 2 α2 mc2 n2 2
s
where we can use some of our previous results. We have already included this factor of 2 in the answer given above. This term is 1/2 the size and of opposite sign. 8 While there is no spin involved here. .
4.4
Perturbation Calculation for H2 Energy Shift
We now calculate the expectation value of H2 . ψnjmj s . we get the probability for the electron and proton to be at the same point.343 Since this does not depend on either m or j. total j states and the product states give the same answer.
which is not deﬁned for
= 0. We will
22. We will choose to use the total j states. We will immediately use the fact that j = ± 1 . we have canceled a term return to this later.4. ψ(0) = 0 for
> 0 and ψ(0) = HD =
for
= 0. HD = h πe2 ¯ 2 3 δ (r) 2m2 c2 e
When we take the expectation value of this. so that we can combine this correction with the spinorbit correction. so
n00
2 h h 4e2 ¯ 2 e2 ¯ 2 α2 m2 c2 2nEn = 2 = mc2 3 a 3 m 2 c2 8n 0 2n3 a0 m2 c2 ¯ h
This is the same as = 0 term that we got for the spin orbit correction. h πe2 ¯ 2 ψ HD  ψ = ψ(0)2 2 c2 2me
√1 2 4π Z na0 3/2
Now.
22. 2 ψnjmj
s H2  ψnjmj s
= =
h ge2 ¯ 2 1 [j(j + 1) − ( + 1) − s(s + 1)] 4m2 c2 2
1 r3
nl
1 ge2 ¯ 2 1 3 1 h ( ± )( + 1 ± ) − ( + 1) − 8m2 c2 2 2 4 a3 0 g¯ h 4m2 c2 a2 0 −En 2mc2 −En 2mc2
(0) 2 En 2 2mc2 2 2
1 n3 ( + 1 )( + 1) 2 1 n ( + 1 )( + 1) 2
= −En = = g 2 g 2 g 2
+ ± ±
1 1 + − 2 4
(+)
2
− −
3 4
h ¯2 ma2 n2 0 h ¯ α m c m¯ 2 n2 h
2 2
−( + 1)
2 2
(−)
n ( + 1 )( + 1) 2
(+)
−( + 1)
(−) 1 2 1 2
n ( + 1 )( + 1) 2
=
n ( + 1 )( +1) 2 −n ( +1) 2
j= + j= −
Note that in the above equation. This actually replaces the = 0 term in the spinorbit correction (which should be zero) making the formula correct!
.5
The Darwin Term
We get a correction at the origin from the Dirac equation.
2 ψnj
mj
Sz  ψnj
mj
=
1 h ¯ β 2 − α2 2
m=mj − 1 2
We can combine the two formulas for j = ± 1 . but we
= =
ψnj
mj
eB (Jz + Sz ) ψnj 2mc
mj
mj
eB h mj ¯ + ψnj 2mc
Sz  ψnj
mj
We already know how to write in terms of these states of deﬁnite m and ms . (1) En
jmj
. = = αY
(mj − 1 ) χ+ 2
Sz  ψnj
mj
+ βY
(mj + 1 ) χ− 2
Sz  αY
(mj − 1 ) χ+ 2
+ βY
(mj + 1 ) χ− 2
1 h ¯ α2 − β 2 2
m=mj − 1 2
For j = − 1 . we must write ψnjmj s in terms of ψn m sms . ψn
jmj
eB Jz ψn 2mc
jmj
=
eB h ¯ mj 2mc
eB The Sz is harder since we are not in eigenstates of that one. 2 ψnj
mj
Sz  ψnj
mj
= =
±
h ¯ 2 h ¯ +m+1− +m α − β2 = ± 2 2 2 +1 1 mj ¯ h h ¯ 2(mj − 2 ) + 1 =± ± 2 2 +1 2 +1
. So.4.6 The Anomalous Zeeman Eﬀect
We compute the energy change due to a weak magnetic ﬁeld using ﬁrst order Perturbation Theory. We need ψn jmj 2mc Sz ψn don’t know how Sz acts on these.344 22. eB (Lz + 2Sz ) ψn 2mc
ψn
jmj
jmj
(Lz + 2Sz ) = Jz + Sz The Jz part is easy since we are in eigenstates of that operator. ψn( ψn(
+ 1 ) (m+ 1 ) 2 2 −1) 2 (m+ 1 ) 2
= =
αY βY
m χ+
+ βY
(m+1) χ− (m+1) χ−
m χ+ − αY
α = β =
+m+1 2 +1 −m 2 +1
Let’s do the j = + ψnj
mj
1 2
state ﬁrst.
we rewrite the ﬁne structure shift. and the socalled Darwin term (due to Dirac equation). Calculate the energy shifts and draw an energy diagram for the n=3 states of Hydrogen. 2.) Clearly list the states in spectroscopic notation and make a diagram showing the allowed electric dipole decays of these states. Now. n = 2. What is the spectrum in the absence of a magnetic ﬁeld? How is the spectrum changed when the atom is placed in a magnetic ﬁeld of 25. (l+
0 2
2. Calculate the ﬁne structure energy shifts (in eV!) for the n = 1. Draw a diagram showing the states before and after the ﬁeld is applied
. the spinorbit interaction. 3. (Note: I am not asking you to derive the equations. we have
(1) En =
eB 2mc
h mj ¯ ±
h mj ¯ 2 +1
=
1 e¯ B h mj 1 ± 2mc 2 +1
for j = ± 1 . Verify the relations used for 1 . spinorbit.000 gauss? Give numerical values for the energy shifts in each of the above cases.345 So adding this to the (easier) part above. Compute the energy shifts in eV.
1 r2 . and n = 3 states of Hydrogen. Calculate the ﬁne structure of hydrogen atoms for spin 1 electrons for n = 1 and n = 2. r l = n − 1.6
Sample Test Problems
4
p 1. − 3 . 2 In summary then. Consider the ﬁne structure of the n = 2 states of the hydrogen atom. You may use ψnlm  1 ψnlm = n21a0 and r ψnlm  r12 ψnlm = n3 a2 1 1 ) . The relativistic correction to the Hydrogen Hamiltonian is H1 = − 8m3 c2 . Calculate and show the splitting of the n = 3 states (as in the previous problem) in a weak magnetic ﬁeld B. 4n
1 2
22. Do not include hyperﬁne splitting or the eﬀects of an external magnetic ﬁeld. 1 1 1 ΔE = − mc2 (Zα)4 3 2 n j+ To this we add the anomalous Zeeman eﬀect ΔE = e¯ B h 1 mj 1 ± 2mc 2 +1 . Include the eﬀects of relativistic corrections. Assume that electrons have spin zero and that there is therefore no spin orbit correction.
and
1 r3
for hydrogen atom states up to n = 3 and for any n if
3. try to estimate the binding energy for the lowest energy n = 2 state including the relativistic. and magnetic ﬁeld.5
Homework Problems
1.
22.
what is the eﬀect of that coupling on the spectrum of 2 r dr an electron bound in a 3D harmonic oscillator? Give the energy shifts and and draw a diagram for the 0s and 1p states. Give algebraic expressions for the energy of each state before the B ﬁeld is applied. 2 ΔEB = e¯ B h 2mc 1± 1 2 +1 mj
. Now a weak magnetic ﬁeld B is applied to hydrogen atoms 2 in the 3d state. V = 1 mω 2 r2 2
dV dr
= mω 2 r
HSO =
h2 1 ¯ 2 2m2 c2 2 [j(j + 1) − l(l + 1) − s(s + 1)]mω 2 2 h ω ¯ HSO = 4mc2 [j(j + 1) − l(l + 1) − s(s + 1)]
1 for the 0S 2 . then. Draw a diagram showing the states before and after the ﬁeld is applied. s = 1 . ΔE = −2 4mc2 . Draw an energy diagram for the n = 3 states. We computed that the energies after the ﬁne structure corrections to the hydrogen spectrum are 2 4 mc2 mc2 4n Enlj = − α2n2 + α8n4 (3 − j+ 1 ). 8. 9. . We label these states in spectroscopic notation: N 2s+1 Lj . 6. . Calculate the energies of all the 3d states (ignoring hyperﬁne eﬀects). Give the energy shift due to the ﬁne structure corrections in units of α4 mc2 . D 2 . the energy only depends on j. According to our calculations of the ﬁne structure. Explain in detail the spectrum of photons before and after the ﬁeld is applied. The energies of photons emitted in the Hydrogen atom transition between the 3S and the 2P states are measured. and s. Calculate the splitting of the n = 3 states of Hydrogen in a weak magnetic ﬁeld B.mj . (10 points) The n = 3 states will split under the standard Hydrogen ﬁne structure. D 2 . 7. Be sure to give an expression for any relevant energy diﬀerences. showing the quantum numbers of the states and the energy splittings.346
4. In Hydrogen. P 2 . If the general form of the spinorbit coupling for a particle of mass m and spin S moving in a potential V (r) is HSO = 2m1 c2 L · S 1 dV .
h ω ¯ 1 for the 1P 2 . with the atoms in a uniform magnetic ﬁeld B. The split states have quantum numbers of j. ΔE = 0. h ω ¯ 3 for the 1P 2 . Give an algebraic expression for the size of the splitting of each state when the ﬁeld is applied. ΔE = +1 4mc2 . Written in spectroscopic notation the states are the n = 3: 2 2 1 2 1 2 3 2 3 2 5 S 2 .
2 2
2
2
5. labeling each state in spectroscopic notation.
They depend only on j = ± 1 . what is the eﬀect of that coupling on the spectrum of 2 r dr an electron bound in a 3D harmonic oscillator? Give the energy shifts and and draw a diagram for the 0p and 1d states. mj . Label each state in spectroscopic notation before the ﬁeld is applied. The ﬁne structure shifts before application of the magnetic ﬁeld are ΔE12 = − 1 4 2 α mc 2n3 1 j+
1 2
−
3 4n
=−
1 4 2 α mc 54
1 j+
1 2
−
1 4
. the n = 3 state is split by ﬁne structure corrections into states of deﬁnite j. ﬁrst with no external ﬁeld. If the general form of the spinorbit coupling for a particle of mass m and spin S moving in a potential V (r) is HSO = 2m1 c2 L · S 1 dV . P 2 . Draw an energy level diagram.
e¯ B 4 h 2mc ( 3 )mj e¯ B 4 h 2mc ( 5 )mj e¯ B 6 h 2mc ( 5 )mj
.347 State 2 1 S2 2 1 P2 2 3 P2 2 3 D2 2 5 D2 Shift before Bﬁeld 1 − 54 3 α4 mc2 4 1 − 54 3 α4 mc2 4 1 − 54 1 α4 mc2 4 1 − 54 1 α4 mc2 4 1 1 − 54 12 α4 mc2 Shift due to Bﬁeld e¯ B h 2mc (2)mj e¯ B 2 h 2mc ( 3 )mj Its easy to diagram from this table.
(The quarks have gyromagnetic ratios of 2 (plus corrections) like the electron but the problem is complicated by the strong interactions which make it hard to deﬁne a quark’s mass. due to the electron’s spin. they are quite measurable and important because they split the ground state.5.
. This particle is actually made up of protons and neutrons which are both spin 1 particles. and the larger magnetic moment. We will calculate ΔE for = 0 states (see Condon and Shortley for more details). Calculating (see section 23. The protons and neutrons in turn are made of spin 1 2 2 quarks. For the proton. 1 S·I n3 ¯ 2 h
ΔE =
e 4 S · B = (Zα)4 mc 3
m MN
(mc2 )gN
Now.348
23
Hyperﬁne Structure
The interaction between the magnetic moment.4.56. just as in the case of the L · S. results in energy shifts which are much smaller than those of the ﬁne me structure. can be used to detect interstellar gas. however. In any case. it is gp ≈ 5. The magnetic moment of the nucleus is μN = ZegN I 2MN c
where I is the nuclear spin vector.1) the energy shift for = 0 states. This is particularly important because it will break the degeneracy of the Hydrogen ground state. which emit radio frequency waves. we should ﬁnd B from μ (see Gasiorowicz page 287) then calculate the energy change in ﬁrst order perturbation theory ΔE = −μe · B . Even though the neutron is neutral.
23. due to the spin of the nucleus. the nuclear gyromagnetic ratio is not just 2. The hyperﬁne corrections may be diﬃcult to measure in transitions between states of diﬀerent n.1
Hyperﬁne Splitting
We can think of the nucleus as a single particle with spin I. Because the nucleus has internal structure. The magnetic dipole moment due to the nuclear spin is much smaller than that of the electron because the mass appears in the denominator. and brieﬂy in Griﬃths 6. To get the perturbation. the gyromagnetic ratio is about 3. This is the nucleus of hydrogen upon which we will concentrate. The diﬀerent hyperﬁne levels of the ground state are populated thermally. we will deﬁne the total angular momentum F = S + I. the nuclear dipole moment is about 1000 times smaller than that for espin or L. This material is covered in Gasiorowicz Chapter 17.) We can compute (to some accuracy) the gyromagnetic ratio of nuclei from that of protons and neutrons as we can compute the proton’s gyromagnetic ratio from its quark constituents. They are of order mp α2 En and are hence called hyperﬁne. Hyperﬁne transitions. spinorbit interaction.83. Chapter XII. in CohenTannoudji et al.
we can drop the orbital term. h ¯
As an examples of perturbation theory. we are doing degenerate state perturbation theory. we choose the set of states in which the larger perturbation is diagonal. For a weak ﬁeld. Since we have already specialized to s states. In essence. the hyperﬁne dominates and we use the states of deﬁnite f .
* See Example 23. The weak ﬁeld limit is achieved if B 500 gauss. we choose our coordinates so that the ﬁeld is in z direction.2
Hyperﬁne Splitting in a B Field
If we apply a Bﬁeld the states will split further. If the two perturbations are of the same order. We could diagonalize the 4 by 4 matrix for the perturbation to solve the problem or we can use what we know to pick the right states to start with. and nuclear spin are considered for now. we can neglect the nuclear magnetic moment in the perturbation. we use the ms . 1 3 3 1 h F 2 − S 2 − I 2 = ¯ 2 f (f + 1) − − 2 2 4 4
S·I =
ΔE = 2 (Zα)4 3
m MN
1 (mc2 )gN n3 f (f + 1) −
3 2
≡
A 2
f (f + 1) −
3 2
For the hydrogen ground state we are just adding two spin
1 2
particles so the possible values are f = 0. for strong ﬁelds. Then we have Wz = 2μB B Sz . 1.9 × 10 . the total angular momentum states will be the right states because we can write the perturbation in terms of quantum numbers of those states. if one perturbation is much bigger than another.1: The Hyperﬁne Splitting of the Hydrogen Ground State. This calculation will always be correct but more time consuming. For ﬁelds achievable in the laboratory.3. we will work this problem for weak ﬁelds. mf states.
. the hyperﬁne splitting is diagonal in states of deﬁnite f while the above perturbation due to the B ﬁeld is diagonal in states of deﬁnite ms .*
The transition between the two states gives rise to EM waves with λ = 21 cm. The perturbation then is ˆ Wz = −B · (μL + μS + μI ) μB B gμN (Lz + 2Sz ) + BIz = h ¯ h ¯
where the magnetic moments from orbital motion. electron spin. In this case. For a strong ﬁeld. Just as in the Zeeman eﬀect. and also work the general case for intermediate ﬁelds.349 It is in the states of deﬁnite f and mf that the hyperﬁne perturbation will be diagonal. Again like the spin orbit interaction.
me We can estimate the ﬁeld at which the perturbations are the same size by comparing μB B to 2 α4 mp mc2 gN = 3 −6 2. we must diagonalize the full perturbation matrix. As usual.
23.
Finally.3. The ﬁgure shows how the eigenenergies depend on B.350 * See Example 23.3. We kept the small term due to the nuclear moment in the B ﬁeld without extra eﬀort.
* See Example 23.3.
2
These should agree with the previous calculations in the two limits: B small.
.
* See Example 23. or B large.*
The result in this case is
E = En00 + 2μB Bms + gμn BmI + Ams mI . In the strong ﬁeld limit we use states ms mi and treat the hyperﬁne interaction as a perturbation. It has the 2 2 hyperﬁne term we computed before and adds a term proportional to B which depends on mf . The unperturbed energies of these states are E = En00 + 2μB Bms + gμN BmI . The four energies are
E = En00 +
A¯ 2 h ± μB B 4
and
A¯ 2 h E = En00 − ± 4
A¯ 2 h 2
2
+ (μB B) .2: The Hyperﬁne Splitting in a Weak B Field. Two of the energy eigenstates mix in a way that also depends on B.*
The result of this is example is quite simple E = En00 + A f (f + 1) − 3 + μB Bmf . we do the full calculation.4: The Hyperﬁne Splitting in an Intermediate B Field.3: The Hyperﬁne Splitting in a Strong B Field.* The general result consists of four energies which depend on the strength of the B ﬁeld.
3
23.1
Examples
Splitting of the Hydrogen Ground State
The ground state of Hydrogen has a spin 1 electron coupled to a spin 1 proton. * See Example 23.6: The Hyperﬁne Splitting in an Intermediate B Field. We have computed in ﬁrst order perturbation theory that ΔE = 2 (Zα)4 3 m MN (mc2 )gN 1 n3 f (f + 1) − 3 2 . This occurs in muonic hydrogen or positronium.
The energy diﬀerence between the two hyperﬁne levels determines the wave length of the radiation emitted in hyperﬁne transitions.*
23. weak field strong field
0
500
B
We can make a more general calculation. this gives
(mc2 )gN
.3.351
E
0
full calc. 1. in which the interaction of the nuclear magnetic moment is of the same order as the electron. giving total angular 2 2 momentum state of f = 0. 4 (Zα)4 3 m MN 1 n3
ΔEf =1 − ΔEf =0 = For n = 1 Hydrogen.3.
84 × 10−6
This transition is seen in interstellar gas. which means the electron’s spin is up and the proton’s spin is down. the upper state is populated so that transitions are possible. 1 μB B ⎝ 0 0 ⎛ 0 0 0 ⎞ 0 0 ⎠ −1
The only nonzero connection between states is between f = 1 and f = 0 and we are assuming the hyperﬁne splitting between these states is large compared to the matrix element. otherwise we should bite the bullet and do the full problem as in the intermediate ﬁeld case.51 938
(. The f = 1 state does emit a photon to deexcite and those photons have a long mean free path in the gas.56) = 5.3. we have to make sure all the matrix elements between those states are zero.352
ΔEf =1 − ΔEf =0 =
4 3
1 137
4
. and because of the small energy diﬀerence.2
Hyperﬁne Splitting in a Weak B Field
Since the ﬁeld is weak we work in the states f mf in which the hyperﬁne perturbation is diagonal and compute the matrix elements for Wz = μB Bσz . Even at a few degrees Kelvin.
23.
. we will have to write those states in terms of ms mi which we will abbreviate like  + − . as we could have guessed.51 × 106 )(5. so the states have about equal population at room temperature. The wavelength is well known.
λ = 2π
1973 h ¯c ˚ = 2 × 109 ˚ = 21.84 × 10−6 eV
1 Recall that at room temperature. Electromagnetic transitions are slow because of the selection rule Δ = ±1 we will learn later. But to do the computation. kB t is about 40 eV. So the full answer is
(1) Ez = μB Bmf
which is correct for both f states.2 cm = 2π A A E 5. The f = 1 state is excited by collisions.
σz 11 = σz ++ = 11 σz 1 − 1 = σz −− = − 1 − 1 1 1 σz 10 = σz √2 (+− + −+ ) = √2 (+− − −+ ) = 00
1 σz 00 = σz √2 (+− − −+ ) = 1 √ 2
(+− + −+ ) = 10
Now since the three (f = 1) states are degenerate. The f = 1 matrix is diagonal.
¯
Recalling that we can write 1 1 S · I = Iz Sz + I+ S− + I− S+ . 2 2 the matrix elements can be easily computed. this assumption free method would be the one to use. The perturbation is Hhf = AS · I where A = 4 (Zα)4 3
me MN 1 1 me c2 gN n3 h2 .3.4
Intermediate Field
Now we will work the full problem with no assumptions about which perturbation is stronger. Note that the terms like I− S+ which change the state will give zero.3 Hydrogen in a Strong B Field
We need to compute the matrix elements of the hyperﬁne perturbation using ms mi as a basis with energies E = En00 + 2μB Bms . This is really not that hard so if we were just doing this problem on the homework.353 23. The reason we work the problem all three ways is as an example of how to apply degenerate state perturbation theory to other problems. ⎜ A¯ 2 h 1 0 ⎝ μB B ⎠ 0 0 4 0 0 h2 0 0 μB B −3A¯ 4
. 4
+ + Hhf  + + =
A¯ 2 h 4 A¯ 2 h 4
− − Hhf  − − =
We can write all of these in one simple formula that only depends on relative sign of ms and mi . E = En00 + 2μB Bms ± A h ¯2 h = En00 + 2μB Bms + A¯ 2 (ms mI ) 4
23.3. 1 1 A + − I · S + − = A + − Iz Sz + I+ S− + I− S+ + − 2 2 = A + − Iz Sz  + − = −A h ¯2 4
− + Hhf  − + = −A
h ¯2 . We continue on as in the last section but work in the states of f mf . The matrix for f mf Hhf + HB f mf is ⎞ ⎛ A¯ 2 h 0 0 0 1 1 4 + μB B ⎟ ⎜ A¯ 2 h 0 0 0 ⎟ 1 −1 ⎜ 4 − μB B ⎟.
We ˙ ˙ ˙ use r ≡ r1 − r2 and p = μr = mr1 −mr2 .354 The top part is already diagonal so we only need to work in bottom right 2 by 2 matrix. 4 Positronium
23.
1 2 2 1 α μc 2 2 n
The relativistic correction must take account of both the motion of the electron and the positron.3. has a “hyperﬁne” correction which is as large as the ﬁne structure corrections since the magnetic moment of the positron is the same size as that of the electron. The zero order energy of positronium states is En = where the reduced mass is given by μ =
me 2 . they are 2
. are E=− A¯ 2 h ± 4 A¯ 2 h 2
2
+ (μB B)2 . Since the electron and positron are of equal mass. we get (A − E)(−3A − E) − B 2 = 0. solving the eigenvalue problem.5
Positronium. In analyzing positronium. the Hydrogenlike bound state of an electron and a positron. The two particles bound together are symmetric in mass and all other properties. It is also an interesting laboratory for the study of Quantum Physics.
The eigenvalues for the other two states which remain eigenstates independent of the ﬁeld strength are A¯ 2 h + μB B 4 and A¯ 2 h − μB B. E 2 + 2AE − 3A2 − B 2 = 0 E= −2A ± 4A2 + 4(3A2 + B 2 ) = −A ± 2 = −A ± 4A2 + B 2 A2 + (3A2 + B 2 )
The eigenvalues for the mf = 0 states. we must take some care to correctly handle the relativistic correction in the case of a reduced mass much diﬀerent from the electron mass and to correctly handle the large magnetic moment of the positron. which mix diﬀerently as a function of the ﬁeld strength. Positronium can decay by anihilation into two or more photons. A B B −3A a b a b
h A ≡ A¯ 4 B ≡ μB B
2
=E
where
Setting the determinant equal to zero.
For positronium. Since p = μv.355 always exactly oposite each other in the center of mass and so the momentum vector we use is easily related to an individual momentum. Lets assume the Thomas precession is also the same. Hrel = − 1 p4 + p4 1 p4 −1 p4 −1 1 2 =− = = 3 c2 3 c2 8 m 4m 32 μ3 c2 8μc2 p2 2μ
2
This is just half the correction we had in Hydrogen (with me essentially replaced by μ). The ﬁnal formula then is HSO = 1 e2 1 ge2 L · S1 + S2 = L · S1 + S2 2 r3 2 2mμc 2 2μ2 c2 r3
again just onehalf of the Hydrogen result if we write everything in terms of μ for the electron spin. A little thinking about signs shows that we just at the positron spin. the hyperﬁne interaction becomes more important. Let’s deﬁne our perturbation W as W ≡ AS1 · S2 + w1 S1z + w2 S2z
. the result is ΔESS = = = 4 αμc 2 e2 2 S · S2 3 2 c2 1 3 2me n h ¯ 2 4 αμc 2 e 8 S1 · S2 3 3 2μ2 c2 n h ¯ 32 4 2 1 S1 · S2 α μc 3 3 n h ¯2
3
3
23.3. We have the same fomula as in the ﬁne structure section except that we have mμ in the denominator. p1 − p2 = p1 p= 2 We will add the relativistic correction for both the electron and the positron. The calculation of the spinspin (or hyperﬁne) term also needs some attention. positronium
We are able to set up the full hyperﬁne (plus B ﬁeld) problem in a general way so that diﬀerent hydrogenlike systems can be handled. we have
HSO =
ge S · p × ∇φ 2mμc2
for the electron. We had ΔESS = 4 2 Ze2 gN S·I 3 3 2me MN c2 n Zαme c h ¯
3
where the masses in the deonominator of the ﬁrst term come from the magnetic moments and thus are correctly the mass of the particle and the mas in the last term comes from the wavefunction and should be replaced by μ. we add the interaction with the positron spin. muonium.
ge The spinorbit correction should be checked also. but. We just need to add the positron.6
Hyperﬁne and Zeeman for H. We know that as the masses become more equal. We had HSO = 2mc2 S · v × ∇φ as the interaction between the spin and the B ﬁeld producded by the orbital motion.
2MN c
Now we use the classical vector potential from a point dipole (see (green) Jackson page 147) 1 A(r) = −(μ × ∇) .
23. which we have so far neglected. r We compute the ﬁeld from this. has a magnetic moment equal to the electron so that it could not be neglected. we have three constants that are determined by the strength of the interactions. ∂ Bk = Aj ∂xi = −μm B =∇×A ∂ 1 ∂ ∂ ∂ =− μm (− mnj ijk = −μm ∂xi ∂xn r ∂xi ∂xn
mnj ikj )
ijk
1 r
∂ ∂ ∂ ∂ ∂ ∂ 1 (δkm δin − δkn δim ) = − μk − μi ∂xi ∂xn r ∂xn ∂xn ∂xi ∂xk B = − μ∇2 1 1 − ∇(μ · ∇) r r
1 r
Then we compute the energy shift in ﬁrst order perturbation theory for s states. ⎛ A¯ 2 h ⎜ ⎜ ⎜ ⎝
4 ¯ + h (w1 + w2 ) 2 0 0 0
1 1 1 0
1 −1 0 0
A¯ 2 h 4
0 h ¯ − 2 (w1 + w2 ) 0 0 A¯ 2 h 2
2
0 0
A¯ 2 h 4 h ¯ 2 (w1
⎞ 0 ⎟ 0 ⎟ ⎟ h ¯ ⎠ 2 (w1 − w2 )
−3A¯ 2 h 4
− w2 )
2
E3 = −
A¯ 2 h + 4
+
h ¯2 (w1 − w2 ) 2
A¯ 2 h − E4 = − 4
A¯ 2 h 2
2
+
h ¯2 (w1 − w2 ) 2
2
Like previous hf except now we take (proton) other B · S term into account. for example.4.356 Here.1
Derivations and Computations
Hyperﬁne Correction in Hydrogen
We start from the magnetic moment of the nucleus μ= ZegN I.4
23. ΔE = e S·B me c =− Ze2 gN 2me MN c2 S · I ∇2 1 r − Si Ij ∂ ∂ 1 ∂xi ∂xj r
. We include the interaction of the “nuclear” magnetic moment with the ﬁeld. This is required because the positron.
Now working out the ∇2 term in spherical coordinates. ∂2 2 ∂ + ∂r2 r ∂r 1 2 2 = 3 + r r r −1 r2 =0
we ﬁnd that it is zero everywhere but we must be careful at r = 0. To ﬁnd the eﬀect at r = 0 we will integrate. d3 r φn00 (r)2 δij ∂ ∂ 1 = ∂xi ∂xj r 3 d3 r φn00 (r)2 ∇2 1 r
So we have ΔE = −
2 Ze2 gN 1 S · I ∇2 3 2me MN c2 r
. (The textbook has numerous mistakes in this section.
4πφn00 (0)2 = Rn0 (0)2 = ΔE =
4 2 Ze2 gN S·I 3 2 3 2me MN c n
Simply writing the e2 in terms of α and regrouping.)
. ΔE = − 2 Ze2 gN S · I(−4πφn00 (0)2 ) 3 2me MN c2 4 n3 Zαme c h ¯ Zαme c h ¯
3 3
1 r
= −4πδ 3 (r). (Basically the derivative with respect to x is odd in x so when the integral is done.
ε ε
∇
r=0
21 3
r
d r=
r=0
1 ∇ · (∇ )d3 r = r
1 (∇ ) · dS = r
∂ 1 dS ∂r r
ε
=
r=0
−1 −1 dS = (4πε2 )( 2 ) = −4π r2 ε
So the integral is nonzero for any region including the origin. which implies ∇2 We can now evaluate the expectation value.357 The second term can be simpliﬁed because of the spherical symmetry of s states. n3 ¯ 2 h
We will sometimes group the constants such that ΔE ≡ AS · I. only the terms where i = j are nonzero). we get ΔE = 4 (Zα)4 3 me MN (me c2 )gN 1 S·I .
Calculate the energies of the four nearly degenerate ground states. 3. Calculate the ﬁne structure of positronium for n = 1 and n = 2. Calculate the shifts in the hydrogen ground states due to a 1 kilogauss magnetic ﬁeld. Find the eigenenergies of the (four) ground states as a function of the B ﬁeld strength.358
23. (The ﬁeld is weak enough so that the perturbation is smaller than the hyperﬁne splitting. a hydrogenlike atom consisting of an electron and a positron (antielectron). (s = 2 with
23. Do not assume that any terms in the Hamiltonian are small. s2 = 1 and l = 4). and (s1 = 1 . A hydrogen atom in the ground state is put in a magnetic ﬁeld. Compute the energy shifts in eV.) 2. 4. Make sure you deﬁne any constants (like A) you use in terms of fundamental constants. Calculate the splitting for the ground state of positronium due to the spinspin interaction between the electron and the positron. Try to correctly use the reduced mass where required but don’t let this detail keep you from working the problem. List the spectroscopic states allowed that arise from combining (s = l = 1). Determine the hyperﬁne structure for the ground state. Calculate the energy shifts to the four hyperﬁne ground states of hydrogen in a weak magnetic ﬁeld. A muonic hydrogen atom (proton plus muon) is in a relative 1s state in an external magnetic ﬁeld.
. Assume that the energy shift due to the B ﬁeld is of the same order as the hyperﬁne splitting of the ground state. 2. 3. Consider positronium. Assume that the perturbation due to the hyperﬁne interaction and the magnetic ﬁeld is given by W = AS1 · S2 + ω1 S1z + ω2 S2z .6
Sample Test Problems
1.5
Homework Problems
1. 2
1 2
with l = 3).
in CohenTannoudji et al. r2 ) = r1e 2  .
. The Hamiltonian has the same terms as Hydrogen but has a large perturbation due to the repulsion between the two electrons. the problem separates into the energy for electron 1 and the energy for electron 2 and we can solve the problem exactly. the electron coulomb repulsion term. u(r1 . H= p2 Ze2 p2 Ze2 e2 1 + 2 − − + 2m 2m r1 r2 r1 − r2 
We can write this in terms of the (Z = 2) Hydrogen Hamiltonian for each electron plus a perturbation. Ignoring V . we will use product states of Hydrogen wavefunctions. usually two neutrons (A = 4).8 eV E12 = E1st = −68. and two electrons bound to the nucleus. H = H1 + H 2 + V where V (r1 .4 eV + 2 .359
24
The Helium Atom
Hydrogen has been a great laboratory for Quantum Mechanics.1
General Features of Helium States
We can use the hydrogenic states to begin to understand Helium. (H1 + H2 )u = Eu We can write these zeroth order energies in terms of the principal quantum numbers of the two electrons. n1 and n2 .
24. Note that V is about the same size as the the rest of the Hamiltonian so −r ﬁrst order perturbation theory is unlikely to be accurate.0 eV E1∞ = Eionization = −54. For our zeroth order energy eigenstates. E = En1 + En2 = − Z 2 α2 me c2 2 n2 n2 n2 n2 1 1
E11 = Egs = −108.2eV Note that E22 is above ionization energy. we get 1 1 1 1 1 + 2 = −54. so the state can decay rapidly by ejecting an electron. This material is covered in Gasiorowicz Chapters 18. Complement BXIV .4 eV E22 = −27. Helium is the simplest atom we can use to begin to study atomic physics. r2 ) = φn1
1 m1 2
(r1 )φn2
2 m2
(r2 )
These are not eigenfunctions of H because of V . Helium has two protons in the nucleus (Z = 2). Recalling that there is a factor of Z 2 = 4 in these energies compared to hydrogen. After Hydrogen. and brieﬂy in Griﬃths Chapter 7.
360
Now let’s look at the (anti) symmetry of the states of two identical electrons. we can make either symmetric or antisymmetric space states. the spatial state is symmetric. 1 (s) u1 = √ (φ100 φ2 2
m
+ φ2
m φ100 ) √
1 (χ+ χ− − χ− χ+ ) 2
1 (t) u1 = √ (φ100 φ2 2
m
− φ2
m φ100 )χ+ χ+
The ﬁrst state is s = 0 or spin singlet. It is very large. so the spin state must be antisymmetric ⇒ s = 0. The second state is s = 1 or spin triplet and has three ms states. Only the +1 state is shown.
. For the ground state. Because the large correction due to electron repulsion is much larger for symmetric space states.
1 u0 = φ100 φ100 √ (χ+ χ− − χ− χ+ ) 2 For excited states. singlet or triplet. We will treat V as a perturbation. the spin of the state determines the energy. We label the states according to the spin quantum numbers. so ﬁrst order perturbation theory will be quite inaccurate.
Higher order perturbation theory would correct this.1) of the energy shift in ﬁrst order involves an integral over the coordinates of both electrons. the s stands for singlet corresponding to the plus sign.3
The First Excited State(s)
Now we will look at the energies of the excited states.361
24.
. A 10% error is not bad considering the size of the perturbation.
24. however.
E1st
(s. even though we neglect all spin contribution in H1 This eﬀect is called the exchange interaction. The Pauli principle will cause big energy diﬀerences between the diﬀerent spin states.975 eV from experiment. Therefore.7.t)
=
Thus we have a large eﬀective spinspin interaction entirely due to electron repulsion. We can write the energy in terms of the Pauli matrices: S1 · S2 σ1 · σ2 = = 1 2 1 3 2 2 2 (S − S1 − S2 ) = s(s + 1) − h ¯ 2 2 2 3 1 triplet 4S1 · S2 /¯ 2 = 2 s(s + 1) − h = −3 singlet 2 1 triplet −1 singlet 1 Jn − (1 + σ1 · σ2 ) Kn 2
1 (1 + σ1 · σ2 ) = 2 E1st
(s. it is hard work doing that inﬁnite sum. We will ﬁnd a better way to improve the calculation a bit.8 eV compared to 78.8 + 34 = −74. There is a large diﬀerence in energy between the singlet and triplet states. the spin triplet energy is lower. In the equation below.t)
=
e2 1 φ100 φ2 m ± φ2 m φ100 φ100 φ2 m ± φ2 m φ100 2 r1 − r2  e2 1 1 = 2 φ100 φ2 m φ100 φ2 m ± 2 φ100 φ2 m φ2 2 r1 − r2  r1 − r2  ≡ J2 ± K2
m φ100
It’s easy to show that K2 > 0. So the ground state energy to ﬁrst order is Egs = −108. ΔEgs = u0 V u0 = = d3 r1 d3 r2 φ100 (r1 )2 φ100 (r2 )2 e2 r1 − r2 
5 Ze2 5 1 5 = Z( α2 mc2 ) = (2)(13.2
The Helium Ground State
Calculating the ﬁrst order correction to the ground state is simple in principle. First order perturbation theory neglects the change in the electron’s wavefunction due to screening of the nuclear charge by the other electron.6) = 34 eV 8 a0 4 2 4 The calculation (see section 24. This is due to the exchange antisymmetry and the eﬀect of the spin state on the spatial state (as in ferromagnetism).
After the perturbation. the ﬁrst excited state is degenerate. This caused early researchers to think that there were two separate kinds of Helium. The diagrams below shows the levels for ParaHelium (singlet) and for OtrhoHelium (triplet).
.
In addition to the large energy shift between the singlet and triplet states.362 The ﬁrst diagram below shows the result of our calculation. Electric Dipole decay selection rules
Δ Δs
= ±1 = 0
cause decays from triplet to singlet states (or viceversa) to be suppressed by a large factor (compared to decays from singlet to singlet or from triplet to triplet). the singlet and triplet spin states split signiﬁcantly due to the symmetry of the spatial part of the wavefunction. Before the perturbation. We designate the states with the usual spectroscopic notation. The second diagrams shows the dominant decay modes. All states increase in energy due to the Coulomb repulsion of the electrons.
363
.
we can vary a test wavefunction. minimizing the energy. E = ψ ∗ Hψdx ψ ∗ Hψ = ψ ∗ ψdx ψψ
∗ ψE HψE dx ∗ ψE ψE dx
. E= For any trial wavefunction ψ. HψE = EψE for the ground state ψE .4
The Variational Principle (RayleighRitz Approximation)
Because the ground state has the lowest possible energy. to get a good estimate of the ground state energy.364
24.
Now we diﬀerentiate with respect to α and evaluate at zero. Conversely. E = ψE + αφHψE + αφ ψE + αφψE + αφ ∂E =0 ∂ψ
Assume α is real since we do this for any arbitrary function φ. E is stationary (2nd order changes only) with respect to variation in ψ. ψ=
E
cE ψE cE 2 E ≥ E0
E =
E
For higher states this also works if trial ψ is automatically orthogonal to all lower states due to some symmetry (Parity. . So our ground state trial function is ψ → φZ (r1 ) φZ (r2 ) .6.5
Variational Helium Ground State Energy
We will now add one parameter to the hydrogenic ground state wave function and optimize that parameter to minimize the energy. 100 100
∗ ∗
.1: Energy of 1D Harmonic Oscillator using a polynomial trail wave function. proving that variations of the energy are second order in variations in the wavefunction.) * See Example 24. it can be shown that E is only stationary for eigenfunctions ψE . We will assume that the wave function changes simply by the replacement Z → Z ∗ < Z. using Gaussian.O. We will start with the hydrogen wavefunctions but allow for the fact that one electron “screens” the nuclear charge from the other.* * See Example 24. Of course the Z in the Hamiltonian doesn’t change. That is. We could add more parameters but let’s keep it simple.2: 1D H..6.. we will add a variable amount of an arbitrary function φ to the energy eigenstate.365 We wish to show that E errors are second order in δψ ⇒ at eigenenergies. We can use the variational principle to approximately ﬁnd ψE and to ﬁnd an upper bound on E0 . To do this. dE dα =
α=0
ψE ψE ( φHψE + ψE Hφ ) − ψE HψE ( φψE + ψE φ ) ψE ψE
2
= E φψE + E ψE φ − E φψE − E ψE φ = 0 We ﬁnd that the derivative is zero around any eigenfunction.*
24.
ψHψ 1 2 2 5 α mc = 2[x] + Z ∗ 4 2 1 5 = − α2 mc2 2Z ∗ 2 − 4Z ∗ (Z ∗ − Z) − Z ∗ 2 4 5 1 = − α2 mc2 −2Z ∗ 2 + 4ZZ ∗ − Z ∗ 2 4
Use the variational principle to determine the best Z ∗ .366 Minimize the energy. We could use more parameters for better results. The correction term is just a constant over r so we can also write that in terms of the hydrogen ground state energy. First. Now we are within a few percent. ∂ ψHψ =0 ∂Z ∗ ⇒ Z∗ = Z − −4Z ∗ + 4Z − 5 =0 4
5 16 Putting these together we get our estimate of the ground state energy. This makes the H1 part just a hydrogen energy.6 eV ) + (Z ∗ − Z)e2 Z∗ a0
d3 r1 φ100 2
1 −Z ∗ 2 α2 mc2 + Z ∗ (Z ∗ − Z)α2 mc2 2 1 2 2 α mc Z ∗ (Z ∗ − Z) − Z ∗ 2 2
Then we reuse the perturbation theory calculation to get the V term.
2
= −77.38 eV
. ψHψ = d3 r1 d3 r2 φ∗ (r1 ) φ∗ (r2 ) 100 100 p2 Ze2 Ze2 p2 e2 1 − + 2 − + φ100 (r1 ) φ100 (r2 ) 2m r1 2m r2 r1 − r2 
We can recycle our previous work to do these integrals.975eV ). replace the Z in H1 with a Z ∗ and put in a correction term.6 eV ) + (Z ∗ − Z)e2 Z ∗ 2 (−13. ψHψ 1 5 = − α2 mc2 Z ∗ −2Z ∗ + 4Z − 2 4 5 5 1 5 = − α2 mc2 (Z − ) −2Z + + 4Z − 2 16 8 4 1 5 = − α2 mc2 2 Z − 2 16 (really − 78. x = = = = = = d3 r1 φ∗ 100 d3 r1 φ∗ 100 p2 Ze2 1 φ100 − 2m r1 p2 Z ∗ e2 (Z ∗ − Z) e2 1 − + 2m r1 r1
φ100 1 r1
Z ∗ 2 (−13.
dE h −3 ¯ 2 1 =0= + mω 2 ⇒ a2 = 2 4 da 2 ma 22 33 √ h ¯2 h ¯ = 33 2 mω mω √ √ 33 + 33 11
√ √ h 3 1 1 33 3 ¯ω h ¯ 2 √ + E = √ + mω 33 = h h ¯ω = ¯ω 2 33 22 mω 22 2 2 33 √ 1 1 4·3 12 = ¯ω √ h h = ¯ω 2 2 11 11
This is close to the right answer. take trial function e−ax energy.
∞
2 2
/2
.367
24. The energy
Now we optimize the parameter.6
24. it is treated as an upper limit on the ground state energy.O. 2 ma2 22
/2¯ 2 h
.6. This should give us the actual ground state
E =
−∞
h ¯ ψ ∗ − 2m ∂ ψ + 1 mω 2 x2 ψ dx ∂x2 2 ∞ −∞
ψ ∗ ψdx
−¯ 2 h 2m
∞ −∞
e−ax
2
a2 x2 − a dx + 1 mω 2 2
∞ −∞
∞ −∞
x2 e−ax dx
2
=
e−ax2 dx
. Recall the actual wave function is e−mωx estimate is 2 2 h2 d 2 a2 − x2  −¯ dx2 + 1 mω 2 x2  a2 − x2 2m 2 E = .2
1D H.6.
24. As always. with exponential wavefunction
2
As a check of the procedure. 2 2 (a2 − x2 )  (a2 − x2 ) We need to do some integrals of polynomials to compute E = h 3 ¯2 1 + mω 2 a2 .1 Use
Examples
1D Harmonic Oscillator
ψ = a2 − x2
2
x ≤ a
2
and ψ = 0 otherwise as a trial wave function.
h h ¯ 2 mω 1 1 mω 2 ¯ + = ¯ω + ¯ω h h 4 mω 4m ¯ h 4 4
24. we gotta do this integral. plug in the Hydrogen ground state wave function (twice).7. ΔEgs 1 4 = 4π Z a0
3 2 ∞ ∞ 2 r1 dr1 e−2Zr1 /a0 0 0 2 r2 dr1 e−2Zr2 /a0
e
2
dΩ1
dΩ2
1 r1 − r2 
.7
24.368
∞
=
1 h −a ¯ + mω 2 2m 2
2 2
x2 e−ax dx + e−ax2 dx
2
−∞ ∞ −∞
h ¯ 2a 2m
∞
e−ax dx =
−∞
2
π √ −1/2 = πa a
∞
−
−∞
x2 e−ax dx =
2
√ 1 π − 2
a−3/2
∞
x2 e−ax dx =
−∞
2
1 2
π 1 = a3 2a
π a
E =
−a¯ 2 h 1 1 h ¯2 h ¯ 2a + mω 2 + = mω 2 + a 4m 4a 2m 4a 4m −mω 2 ∂E h ¯2 = =0 + 2 ∂a 4a 4m 4a2 ¯ 2 = 4m2 ω 2 h mω a= h ¯
h ψ = e− 2¯ mω
x2
E = OK. ΔEgs = u0 V u0 = d3 r1 d3 r2 φ100 (r1 )2 φ100 (r2 )2 e2 r1 − r2 
First.1
Derivations and Computations
Calculation of the ground state energy shift
To calculate the ﬁrst order correction to the He ground state energy.
369 1 = r1 − r2  Do the dΩ1 integral and prepare the other. ΔEgs = 4π 2 e π2 4π 2 e π2 Z a0 Z a0
6 ∞ 2 r1 dr1 e−2Zr1 /a0 0 ∞ 2 r1 dr1 e−2Zr1 /a0 0 2 2 − r1 + r2 − 2r1 r2 + 0 2 2 r1 + r2 + 2r1 r2 ∞ 2 r1 dr1 e−2Zr1 /a0 0 ∞ 2 r2 dr2 e−2Zr2 /a0 0 ∞ 2 r2 dr2 e−2Zr2 /a0 ∞ 2 r2 dr2 e−2Zr2 /a0 2π
−2 2r1 r2
1 2 2 r1 + r2 − 2r1 r2 cos θ2 −1
6
ΔEgs
=
2π r1 r2
ΔEgs
=
4π 2 e π2 8e2
Z a0 Z a0
6
6
∞
2π [−r1 − r2  + (r1 + r2 )] r1 r2
0 ∞
ΔEgs
=
r1 dr1 e−2Zr1 /a0
0 0
r2 dr2 e−2Zr2 /a0 (r1 + r2 − r1 − r2 )
We can do the integral for r2 < r1 and simplify the expression. Because of the symmetry between r1 and r2 the rest of the integral just doubles the result. ΔEgs = 16e
2
Z a0
∞
6
∞
r1
r1 dr1 e
0 x1
−2Zr1 /a0 0
r2 dr2 e−2Zr2 /a0 (2r2 )
ΔEgs
= e2
Z a0
2
x1 dx1 e−x1
0 ∞
x2 dx2 e−x2 2
=
=
0 ⎧ ⎫ x1 ⎨ ⎬ Ze x1 dx1 e−x1 −x2 e−x1 + 2x2 dx2 e−x2 ⎩ 1 ⎭ a0 0 0 ⎧ ⎫ x1 ∞ ⎨ ⎬ Ze2 x1 dx1 e−x1 −x2 e−x1 − 2x1 e−x1 + 2 e−x2 dx2 ⎩ 1 ⎭ a0
=
Ze a0
2
0 ∞
0
x1 dx1 e−x1 −x2 e−x1 − 2x1 e−x1 − 2 e−x1 − 1 1
0 ∞
Ze2 = − a0
x3 + 2x2 + 2x1 e−2x1 − 2x1 e−x1 dx1 1 1
0
. ΔEgs 4π = 2 e2 π Z a0
6 ∞ 2 r1 dr1 e−2Zr1 /a0 0 0 ∞ 2 r2 dr2 e−2Zr2 /a0
1
2 r1
+
2 r2
− 2r1 r2 cos θ
dφ2 d cos θ2
1
2 r1
+
2 r2
− 2r1 r2 cos θ2
The angular integrals are not hard to do.
We wish to get a good upper limit on the Helium ground state energy. This problem is set up in the discussion of the ﬁrst excited states (See section 24. this sets us up to do our integrals nicely. Use the variational principle to estimate the ground state energy of the anharmonic oscillator.23 MeV for the nuclear ground state. The binding energy is found to be 2.8 Fermis. m
2. p2 H = 2m + λx4 . 1.l where = 0. φ1 )Y (−m) (θ2 .6 eV ) → 34 eV for Z=2 4
= − ΔEgs
24.t) ΔE2. Consider the lowest state of orthohelium. 4. P (cos θ12 ) = Using the equation Y 4π 2 +1 (−1)m Y
m=− m (θ1 . Use the variational principle with a gaussian trial wave function to prove that a one dimensional attractive potential will always have a bound state.3). 1 = r1 − r2 
∞ =0
r< P (cos θ12 ) +1 r>
Here r< is the smaller of the two radii and r> is the larger. an = 0 state. The integral (1s)2  r1e 2  (1s)2 = 5 Z ∗ α2 mc2 for a −r 8 nucleus of charge Z ∗ e. we can expand the formula for the inverse distance between the two electrons as follows. Then we can use a version of the addition theorem to write the Legendre Polynomial P (cos θ12 ) in terms of the spherical hamonics for each electron. Determine 2 the value of Z ∗ which gives the best limit. A proton and neutron are bound together into a deuteron. the nucleus of an isotope of hydrogen. Assuming −r/r0 a potential of the form V (r) = V0 e r/r0 .
24. As in the ground state calculation. use the variational principle to estimate the strength of the potential. Calculate the lowest order energy shift for the (0th order degenerate ﬁrst) excited states of Helium (s. we can use the symmetry of the problem to specify which radius is the larger. φ2 )
(−m)
= (−1) Y ∗ . What is the magnetic moment? That is what is the interaction with an external magnetic ﬁeld? 3. Use as a trial wave function the 1s hydrogen state with the parameter a screened nuclear charge Z ∗ to get this limit. with r0 = 2.9
Sample Test Problems
1. First.
. The following formulas will aid you in the computation.370 211 11 11 Ze2 3 2 1 1 +2 +2 −2 a0 2 2 2 2 222 22 11 Ze2 3 4 4 16 5 Ze2 + + − = − =+ a0 8 8 8 8 8 a0 5 = Z(13. 5.8
Homework Problems
1.
Calculate the energy of this state to zeroth order in the perturbation V. A Helium atom has two electrons bound to a Z = 2 nucleus. H= Ze2 Ze2 p2 p2 e2 1 − = H1 + H2 + V + 2 − + 2m r1 2m r2 r1 − r2 
The ﬁrst excited state of Helium has one electron in the 1S state and the other in the 2S state. The possible total spin states are s = 0 and s = 1. Don’t do any integrals. Make sure to take account of the Pauli principle in your states. Give the answer in eV. Write out the full ﬁrst excited Helium state which has s = 1 and ms = −1. Use braket notation to calculate the energy shift to this state in ﬁrst order perturbation theory.371 2. The spins of the two electrons can be added to give states of total spin S. The lowest energy excited states of Helium have the electrons in a (1s)(2s) conﬁguration in space and can have total spin 0 or 1. Include the spatial wave function and don’t forget the Pauli principle. Which state will have the lower energy?
. We have to add the coulomb repulsion term (between the two electrons) to the zeroth order Hamiltonian. Write out the full (space and spin) states for a) s = 1 and ms = 0 and for b) s = 0 and ms = 0. 3.
Because of the Pauli principle. 3d. 4s. From lowest to highest energy. φ)2 = 4π
m=−
With all the states ﬁlled and the relative phases determined by the antisymmetry required by Pauli. 4f. The states we have from hydrogen are modiﬁed signiﬁcantly. which is antisymmetric under interchange. to have lower energy than the 4f or 5d states. we can put only one electron into each state. Adding these together gives a total spin state with s = 0. Because of the screening. must by symmetric in space and hence antisymmetric in spin. The spatial state must be totally symmetric under interchange and. 5p. it even moves the 6s state. When we have enough electrons to ﬁll a shell. Electrons which are far away from the nucleus see less of the nuclear charge and shift r up in energy. the quantum numbers of the closed shell are determined. 6p. 3s. 3p. 6s. since all the states in the shell have the same n and . the atomic shells have the order 1s. 5s. 2m ri ri − rj  i=1 i>j We have seen that the coulomb repulsion between electrons is a very large correction in Helium and that the three body problem in quantum mechanics is only solved by approximation. This implies each pair of electrons has a total spin of 0. the two electrons in the same spatial state. As in Helium.1
Atomic Shell Model
The Hamiltonian for an atom with Z electrons and protons is ⎡ ⎤ Z p2 Ze2 e2 ⎦ i ⎣ − + ψ = Eψ. for example. 2p. There is only one possible state representing a closed shell. and in CohenTannoudji et al. This can be shown to give us a total = 0 state. The eﬀect of screening not only breaks the degeneracy between states with the same n but diﬀerent . Complement AXIV .
25. the potential no longer has a pure 1 behavior. So the closed shell contributes a spherically symmetric charge and spin distribution with the quantum numbers s=0 =0 j=0 The closed shell screens the nuclear charge. 4p. Y m (θ. This is a large eﬀect and single electron states with larger have larger energy. What hope do we have to understand even more complicated atoms? The physics of closed shells and angular momentum enable us to make sense of even the most complex atoms. it is the diﬀerent m states which are symmetrized. 4d. φn m . say the 1s or 2p. The resulting electron distribution is spherically symmetric because 2 +1 . The 4s and 3d states have about the same energy in atoms because of screening. 2s.372
25
Atomic Physics
This material is covered in Gasiorowicz Chapter 19.
. 5d.
For example. For very heavy atoms. Couple the valence electrons (or holes) to give maximum total spin. we add the total angular momentum from each electron ﬁrst then add up the Js. however. it is useful to know how one might proceed to solve more diﬃcult problems. This equation depends on the wavefunctions of the other electrons but can be solved in a self consistent way using the variational principle and iterating. Since we will not apply these equations o to solve problems. εi represents the energy contribution of electron i.2
The Hartree Equations
The Hartree method allows us to to change the 3Z dimensional Schr¨dinger equation (Z electrons in o 3 dimensions) into a 3 dimensional equation for each electron. The equation is derived (see Gasiorowicz pp 309311) from the Schr¨dinger equation using ψ = φ1 φ2 . In this equation we can formally see the eﬀect of screening by the other electrons. . spin 1 holes. . help us determine the quantum numbers for the ground states of atoms. We get a great simpliﬁcation by treating nearly closed shells as a closed shell plus positively charged.
. The Pauli principle rather than the rule. . If the shell is more than half full. we will not go into the derivation. For heavy atoms.)
1. if an 2 atom is two electrons short of a closed shell. is called LS or RusselSaunders coupling.
25. This method of adding up all the spins and all the Ls. As we add valence electrons we follow Hund’s rules to determine the ground state. φZ . and hence the positive contribution to the energy. Now choose the state of maximum (subject to the Pauli principle. The hydrogenic shells ﬁll up giving well deﬁned j = 0 states for the closed shells. This method and these rule are quite good until the electrons become relativistic in heavy atoms and spinorbit eﬀects become comparable to the electron repulsion (arond Z=40). An improved formalism known as the HartreeFock equations. we treat it as a closed shell plus two positive holes.373
25. ψ = φ1 (r1 ) φ2 (r2 ) . Thus we need to use states in which the total angular momentum of each electron is a good quantum number. We choose the states in which the total s and the total are good quantum numbers are best for minimizing the overlap of electrons. accounts for the required antisymmetry and gives slightly diﬀerent results. often determines everything here.) 3.3
Hund’s Rules
A set of guidelines. This is called jj coupling. The term e2
j=i
d3 rj
φj (rj )2 ri −rj 
represents the potential due to the other electrons in which electron i moves. 2. known as Hund’s rules. pick the highest total angular momentum state j = +s otherwise pick the lowest j =  − s. electrons are relativistic and the spinorbit interaction becomes more important than the eﬀect of electron repulsion. φZ (rZ ) ⎡ ⎤ 2 2 2 h φj (rj ) ⎦ ⎣ −¯ ∇2 − Ze + e2 φi (ri ) = εi φi (ri ) d3 rj 2m i ri ri − rj 
j=i
In the Hartree equation above. .
who can’t understand addition of angular momentum. requiring an antisymmetric spatial wavefunction which has a lower energy as we showed for Helium.6. A simpler set of rules has been developed for chemists. the larger the total the more lobes there are in the overall electron wavefunction and the lower the eﬀect of electron repulsion.3: 25. The maximum spin state is symmetric under interchange.
1. We can put two electrons into each space. It is based on the same principles. The only way to have a totally antisymmetric state is to have no two electrons in the same state. Make as many spins as possible parallel. but. larger j increases the energy.* Oxygen ground State. then compute ms and call that s. Fill the table with the number of valence electrons according to the following rules.* Carbon ground State. We have not demonstated it.6. that is. and call this .6. We use the same kind of trick we used to get a feel for addition of angular momentum.
. one with spin up and one with spin down.*
25.374 We can understand Hund’s rules to some extent. The reverse is true for holes which have an eﬀective postive charge.1: 25.4
The Periodic Table
The following table gives the electron conﬁgurations for the ground states of light atoms.* Nitrogen ground State. Now set the orbital states to make maximum m . Make a table with space for each of the diﬀerent m states in the outer shell. we look at the maximum z component we can get consistent with the Pauli principle. but don’t allow any two electrons to be in the same state (of ms and m ).
3.
This method is rather easy to use compared to the other where addition of more than two angular momenta can make the symmetry hard to determine.6. Couple to get j as before.
2.4: The The The The Boron ground State. For electrons with their negative charge. Now the spin orbit interaction comes into play. * * * * See See See See Example Example Example Example 25.2: 25.
0 15.
. as the elctron gains binding energy from more positive charge in the the nucleus without much penalty from repulsion of the other electrons in the shell. 6s. the atom shrinks in size and becomes more tightly bound.6 5. A single electron outside a closed shell often has the lowest Ionization Potential because it is well screened by the inner electrons.8 6. 2p.4 13.1 7. 2s.7
We see that the atomic shells ﬁll up in the order 1s.375 Z 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 36 54 86 El. The ﬁgure below shows a plot of ionization potential versus Z. 4d. 3s.3 11. 13.6 5. H He Li Be B C N O F Ne Na Mg Al Si P S Cl Ar K Ca Sc Ti V Cr Mn Fe Kr Xe Rn Electron Conﬁguration (1s) (1s)2 He (2s) He (2s)2 He (2s)2 (2p) He (2s)2 (2p)2 He (2s)2 (2p)3 He (2s)2 (2p)4 He (2s)2 (2p)5 He (2s)2 (2p)6 Ne (3s) Ne (3s)2 Ne (3s)2 (3p) Ne (3s)2 (3p)2 Ne (3s)2 (3p)3 Ne (3s)2 (3p)4 Ne (3s)2 (3p)5 Ne (3s)2 (3p)6 Ar (4s) Ar (4s)2 Ar (4s)2 (3d) Ar (4s)2 (3d)2 Ar (4s)2 (3d)3 Ar (4s)(3d)5 Ar (4s)2 (3d)5 Ar (4s)2 (3d)6 (Ar) (4s)2 (3d)10 (4p)6 (Kr) (5s)2 (4d)10 (5p)6 (Xe) (6s)2 (4f )14 (5d)10 (6p)6
2s+1 2
Lj
S1/2 S0 2 S1/2 1 S0 2 P1/2 3 P0 4 S3/2 3 P2 2 P3/2 1 S0 2 S1/2 1 S0 2 P1/2 3 P0 4 S3/2 3 P2 2 P3/2 1 S0 2 S1/2 1 S0 2 D3/2 3 F2 4 F3/2 7 S3 6 S3/2 5 D4 1 s0 1 s0 1 s0
1
Ioniz. The Ionization Potential peaks for atoms with closed shells.0 12.9 14. 3p.7 6. 4s. Its no wonder that the periodic table is not completely periodic.6 24. 4p. 4f.4 21.6 6.5 6. 5p. essentially the Binding energy of the last electron.4 9.1 6. 3d.1 11. 5s. As charge is added to the nucleus.7 7.6 17. The eﬀect of screening increasing the energy of higher states is clear. Pot.3 8.4 7.0 8. 6p.1 10.8 4.3 6.0 10.3 14.5 13.
The Ionization Potential column gives the energy in eV needed to remove one electron from the atom. 5d.
376
.
1.377
The perodic table of elements is based on the fact that atoms with the same number of electrons outside a closed shell have similar properties. 2s. 4p 5. the periodicity is broken and special “series” are inserted to contain the 4f and 5f shells. 3s. Even with the strong nuclear force. 3d.
25. This is based on angular momentum and the Pauli principle. 2p 3. The rows of the periodic table contain the following states. a shell model describes important features of nuclei. 4s. 3p 4. 5s. Tightly bound nuclei correspond
. It works because of the tight binding and simplicity of closed shells. Nuclei have tightly bound closed shells for both protons and neutrons.5
The Nuclear Shell Model
We see that the atomic shell model works even though the hydrogen states are not very good approximations due to the coulomb repulsion between electrons. 5p Soon after. 4d. 1s 2.
as indicated in the ﬁgure below. What elements exist is governed by nuclear physics and we can get a good idea from a simple shell model. 82 Pb208 is a good example of a doubly magic nucleus with many more neutrons than protons. It is this eﬀect and the shell model for which Maria Mayer got her Nobel prize.378 to the most abundant elements. Heavier nuclei tend to have more neutrons than protons because of the coulomb repulsion of the protons (and the otherwise symmetric strong interactions). Nuclear magic numbers occur for neutron or proton number of 2. The splitting between states of diﬀerent j is smaller than that but of the same order as splitting between radial or angular excitations. 82. 8. Nuclei where the number of protons or neutrons is magic are more tightly bound and often more abundant. Nuclei which are doubly magic are very tightly bound compared to neighboring nuclei. 50. 28. 20. The other feature of note in the nuclear shell model is that the nuclear spin orbit interaction is strong and of the opposite sign to that in atoms. and 126. its only hydrogen states which are labeled with a principle quantum number n = nr + + 1. 9 In the nuclear shell model. Remember.
. n refers only to the radial excitation so states like the 1h 2 show up in real nuclei and on the following chart.
m 1 0 1 s= =
e ↑ ↑ ms = 1 m =1
We can take a look at the excited states of carbon to get an appreciation of Hund’s rules. Electric dipole transitions are shown changing by one unit. tells us to couple the two electron spins to s = 1. 1. maximum . The maximum state is symmetric. The following chart shows the states of a carbon atom. This is the symmetric spin state so we’ll need to make the space state antisymmetric. we get total = 0. For most states. The valence electron is in the 2P state and hence has = 1 and s = 1 . the next antisymmetric. maximum total s. 2 2 m 1 0 1 s= = e ↑ ms = 1 2 m =1
25. They add up to j = 0 as do all closed shells. So the ground state is 3 P0 . This means = 1 is the only option. 2. Hund’s second rule. So nuclear isotopes with odd numbers of protons or odd numbers of neutrons have less binding energy and nuclei with odd numbers of both protons and neutrons are unstable (with one exception). Remember.379 Another feature of nuclei not shown in the table is that the spinspin force very much favors nucleons which are paired. So the ground state is 2 P 1 .6. and the = 0 state is again symmetric under interchange. with Z = 6 has the 1S and 2S levels ﬁlled giving j = 0 as a base.
25. a basis of (1s)2 (2s)2 (2p)1 is assumed and the state of the sixth electron is given. Since the shell is not half full we 2 couple to the the lowest j =  − s = 1 .
. It has two valence 2P electrons. The simpler way works with a table.1
Examples
Boron Ground State
Boron. Some states have other excited electrons and are indicated by a superscript. Since the shell is not half full we couple to the the lowest j =  − s = 0.6
25. with Z = 5 has the 1S and 2S levels ﬁlled. Diﬀerent j states are not shown since the splitting is small. adding two P states together.6.2
Carbon Ground State
Carbon. doesn’t play a role because only the = 1 state is antisymmetric. Hund’s ﬁrst rule .
and = 1. They are both spin singlets so its the symmetry of the space wavefunction that is making the diﬀerence here. 1. maximum total s. doesn’t play a role. This is again the symmetric spin state so 2 we’ll need to make the space state antisymmetric. All I have to say is 3 ⊗ 3 ⊗ 3 = 7S ⊕ 5MS ⊕ 3MS ⊕ 5MA ⊕ 3MA ⊕ 1A ⊕ 3MS . Here MS means mixed symmetric. tells us to couple the three electron spins to s = 3 . it is symmetric under the interchange of two of the electrons but not with the third. = 0. with Z = 7 we have three valence 2P electrons and the shell is half full. 1.6. Hund’s second rule.380
The ground state has s = 1 and = 1 as we predicted. 2. 3 for 12 = 2. maximum . That is. Hund’s ﬁrst rule .3
Nitrogen Ground State
Now. 2 for 12 = 0. again.
25. because 12
. Other states labeled 2p are the ones that Hund’s ﬁrst two rules determined to be of higher energy. Adding another P state to each of these gives total = 1. adding two P states together. 2. we get total = 1 for 12 = 0. Remember. We now have the truly nasty problem of ﬁguring out which total states are totally antisymmetric.
381 only the = 0 state is totally antisymmetric. So the ground state is 4 S 3 . Since the shell is just half full we couple to the the lowest j =  − s = 3 . Our prediction of the ground state is again correct and a few space symmetric states end up a few eV higher than the ground state. Note that the chart method is clearly easier to use in this case.
. 2 2
m 1 0 1 s= =
e ↑ ↑ ↑ ms = 3 2 m =0
The chart of nitrogen states is similar to the chart in the last section.
It has four valence 2P electrons which we will treat as two valence 2P holes. Write the state in spectroscopic notation. with Z = 8 has the 1S and 2S levels ﬁlled giving j = 0 as a base. Use Hund’s rules to ﬁnd the spectroscopic description of the ground states of the following atoms: N(Z=7). Sc(Z=21). K(Z=19). List the possible spectroscopic states that can arise in the following electronic conﬁgurations: (1s)2 . Use the standard 2s+1 Lj notation. (2p)2 . So the ground state is 3 P2 . 2.6. maximum total s. 24. tells us to couple the two hole spins to s = 1. 3. 34. Hund’s ﬁrst rule . How many energy levels are there now? What is the gyromagnetic ratio for the ground state of Florine. Also determine the electronic conﬁguration. maximum . m 1 0 1 s= = e ↑↓ ↑ ↑ ms = 1 m =1
25. L.8
Sample Test Problems
1. (Ignore the spin of the nucleus. 3. Since the shell is more than half full we couple to the the highest j = + s = 2.) A weak magnetic ﬁeld is applied splitting the state. Use Hund’s rules to check the (S. doesn’t play a role because only the = 1 state is antisymmetric. Co(Z=27). A Florine (Z=9) atom is in its ground state.
25. J) quantum numbers of the elements with Z =14. Which should be the ground state? 2. and (3d)4 .
. Take the exclusion principle into account. This is the symmetric spin state so we’ll need to make the space state antisymmetric.4 Oxygen Ground State
Oxygen. Write down the ground state (in spectroscopic notation) for the element Oxygen (Z = 8).382 25. Write down the electron conﬁguration and ground state for the elements from Z = 1 to Z = 10. 15.7
Homework Problems
1. (2p)4 . 30. (2p)3 . Hund’s second rule.
We must compute the normalization constant to estimate the energy. around nucleus A. The lowest energy wavefunction can be thought of as a (anti)symmetric linear combination of an electron in the ground state near nucleus A and the ground state near nucleus B ψ± r.
. Complements CV I. ψA and ψB are not orthogonal. E ∼ 0. Entire molecule rotates. we will study the binding and excitation of simple molecules. thus reducing the kinetic energy. there is overlap. EV II .1
The H+ Ion 2
The simplest molecule we can work with is the H+ ion. R = C± (R) [ψA ± ψB ] where ψA =
1 −r1A /a0 e πa3 0
is g. 1 2 = ψA ± ψB ψA ± ψB = 2 ± 2 ψA ψB ≡ 2 ± 2S(R) C± where S(R) ≡ ψA ψB = 1+ R R2 + 2 a0 3a0 e−R/a0
These calculations are “straightforward but tedious” (Gasiorowicz). e2 p2 e2 e2 − + H0 = e − 2m r1A r1B RAB RAB is the distance between the two nuclei. CXI .383
26
Molecular Physics
In this section. and in CohenTannoudji et al. Nuclei move slowly in background of electrons. Atoms bind into molecules by sharing electrons. • Excitation of electrons to higher states. E ∼ 0.s. Molecules can be excited in three ways. E ∼ 4 eV • Vibrational modes (Harmonic Oscillator).1 eV • Rotational modes (L = n¯ ). It has two nuclei (A and B) sharing one electron 2 (1).001 eV h Why don’t atoms have rotational states? The atomic state already accounts for electrons angular momentum around the nucleus.
26. About which axes can a molecule rotate?
Do you think identical atoms will make a diﬀerence?
This material is covered in Gasiorowicz Chapter 20.
6 eV so there is no binding in this state.
The graph below shows the energies from our calculation for the space symmetric (Eg ) and antisymmetric (Eu ) states as well as the result of a more complete calculation (Exact Eg ) as a function of the distance between the protons R. We could get a better estimate by introduction some parameters in our trial wave function and using the variational method. and hence.384 We can now compute the energy of these states. Now.76 eV.3 Angstroms between the nuclei and a Binding Energy of 1.
ψA H0 ψA ψA H0 ψB
= =
E1 +
e2 R e−2R/a0 1+ R a0 e2 R e2 E1 + 1+ S(R) − R a0 a0
e−R/a0
We have reused the calculation of S(R) in the above. Our calculation for the symmetric state shows a minimum arount 1.
The antisymmetric state shows no minimum and never goes below 13.
E1 + H0 H0
±
= = E1
e2 R
(1 + R/a0 ) e−2R/a0 ± E1 +
−2y
e2 R
S(R) −
e2 a0
(1 + R/a0 ) e−R/a0
1 − (2/y)(1 + y)e
±
1 ± S(R) ± (1 − 2/y)(1 + y + y 2 /3)e−y − 2(1 + y)e−y 1 ± (1 + y + y 2 /3)e−y
The symmetric (bonding) state has a large probability for the electron to be found between nuclei. the distance between the atoms in units of the Bohr radius. The antisymmetric (antibonding) state has a small probability there.
. a much larger energy. we plug these in and rewrite things in terms of y = R/a0 .
H0
±
= = =
1 ψA ± ψB H0 ψA ± ψB 2[1 ± S(R)] 1 [ ψA H0 ψA + ψB H0 ψB ± ψA H0 ψB ± ψB H0 ψA ] 2[1 ± S(R)] ψA H0 ψA ± ψA H0 ψB 1 ± S(R)
We can compute the integrals needed.
8 eV
Its clear we would need to introduce some wfn. protonA . parameters to get good precision.385
By setting
d H dy
= 0. ψ(r1 . the repulsion between electrons. The Hamiltonian can be written in terms of the H+ Hamiltonian.
Calculated Actual
Distance 1.3 ˚ A 1. e2 . r2 ) = 1 [ψA (r1 ) + ψB (r1 )] [ψA (r2 ) + ψB (r2 )] χs 2[1 + S(RAB )]
.06 ˚ A
Energy 1.76 eV 2. and protonB . H = H1 + H 2 + H1 = e2 e2 − r12 RAB
e2 p2 e2 e2 1 − − + 2m rA1 rB1 RAB
We wish to compute variational upper bound on RAB and the energy. We will again use symmetric electron wavefunctions.2
The H2 Molecule
The H2 molecule consists of four particles bound together: e1 . plus a correction 2 term for double counting the repulsion between protons. we can get the distance between atoms and the energy.
26.
386 where the spin singlet is required because the spatial wfn is symmetric under interchange. ψHψ = 2EH + (RAB ) −
2
e2 e2 ψ + ψ RAB r12
From this point. The space symmetric state will be the ground state as before. in a bonding state.
wIth a multiterm wavefunction. Unpaired electrons don’t have this problem. Therefore only the antibonding (or some excited state) will work and binding is unlikely. If we try to share one of the paired electrons.4
Molecular Orbitals
Even with additional parameters. ±1. The symmetric or bonding state has a larger probability to be between the two nuclei. The m = 0. Pictures of molecular orbitals are shown for s and p states in the following ﬁgure. Imagine that a valence electron is in a d state.68 eV 4. This means Lz commutes with H and m is a good quantum number.
26.85 ˚ A 0. The outer (valence) electrons may participate in bonding either by sharing or migrating to the other atom.3
Importance of Unpaired Valence Electrons
Inner (closed shell) electrons stick close to nucleus so they do not get near to other atoms. we can do the calculation to obtain
Calculated Actual
Distance 0. δ respectively. . with another atom. and is therefore lower energy. .
26. the kinetic energy can be lowered by sharing an electron.74 ˚ A
Energy 2. Each has a bonding and an antibonding state. Electrons which are paired into spin singlets don’t bond.f). we could get good agreement. we have seen. have quite diﬀerent shapes therefore bond diﬀerently. There is an axis of symmetry for diatomic molecules.75 eV. π. The diﬀerent m states.
. Both bonding and antibonding orbitals are shown ﬁrst as atomic states then as molecular. the electron from the other atom is not antisymmetric with the (other) paired electron. ±2 are called molecular orbitals σ. The antibonding states are denoted by a *. ↓↑ ↓↑ ↑ . sees more positive charge. ﬁrst four don’t bond! The strongest bonds come from s and p orbitals (not d. parity symmetry in diatomic molecules implies we will have symmetric and antisymmetric wavefunctions for single electrons. As in our simple model of a molecule.
387
.
. proton has the same spring constant k ≈ h ¯ Evib ∼ ¯ h Recalling that room temperature is about energy levels are simply k = M
1 40 k me . The graph below shows the energy spectrum of electrons knocked out of molecular hydrogen by UV photons (photoelectric eﬀect). h ¯ We can estimate the energy of the vibrational levels. infrared. Diatomic molecules have just one. The diﬀerent peaks correspond to the vibrational state of the ﬁnal H+ ion. this is approximately thermal energy.
then crudely the
m 1 Ee ∼ eV M 10
eV. 2
Can you calculate the number of vibrational modes for a molecule compose of N > 3 atoms. The
1 E = (n + )¯ ωvib h 2 Complex molecules can have many diﬀerent modes of vibration. This looks just like a harmonic oscillator potential for small variations from the minimum.388
26. The molecule can “vibrate” in this potential giving rise to a harmonic oscillator energy spectrum. If Ee ∼ ¯ ω = h √ √ E e me .5
Vibrational States
We have seen that the energy of a molecule has a minimum for some particular separation between atoms.
three moments of inertia to use in our quantized formula.
These states are strongly excited at room temperature. is required to be even for (nuclear) spin singlet and odd for triplet. which should be equal to the number of quantum numbers needed to describe the state. With identical nuclei. we have 3 coordinates to give the position of the center of mass. and 3N6 for vibrational. Counting degrees of freedom. This formula should be modiﬁed if the molecule is too simple to have three principle axes. and hence. The graph below shows the absorption coeﬃcient of water for light of various energies.
E=
( + 1)¯ 2 h 2I
ΔE =
h ¯2 h ¯2 h ¯2 [ ( + 1) − ( − 1) ] = (2 ) = 2I 2I I
These also have equal energy steps in emitted photon energy. rotational and vibrational states cause the absorption of light.389
26. It is only in the region around the visible spectrum that water transmits light well.
Let’s look at the energy changes between states as we might get in a radiative transition with Δ = 1. 3 for the rotational state. For low energies. electronic excitation and photoelectric eﬀect take over. Can you think of a reason for that?
. steps will be larger. At higher energies. We can estimate the energy of these rotations to be h
Erot =
( + 1)¯ 2 h h ¯2 m 1 1 L2 m α2 mc2 = ≈ ≈ E≈ eV = 2 I 2I 2M a2 M 2 M 1000 0
where we have used a0 =
h ¯ αmc .6
Rotational States
Molecules can rotate like classical rigid bodies subject to the constraint that angular momentum is quantized in units of ¯ .. This means
A complex molecule will have three principle axes.
103. 2. What is the energy diﬀerence between the lowest and ﬁrst excited rotational states in eV?
.8 26.51 and 185. 124.7 26. In HCl.30. What is the ratio of the number of HCl molecules in the j = 10 rotational state to that in the j = 0 state if the gas is at room temperature?
26.10
Sample Test Problems
1. absorption lines with wave numbers in inverse centimeters of 83.86 have been observed.390
26. 165.9
Examples Derivations and Computations Homework Problems
1. Are these rotational or vibrational transitions? Estimate some physical parameters of the molecule from these data.05. Find an expression for the rotational energies of an O2 molecule. 145. Oxygen has Z=8 and A=16.73.03.
⎛ ⎞ ∂cn (t) 1 ⎝ = Vni (t)eiωni t + Vnk (t)ck (t)eiωnk t ⎠ ∂t i¯ h
k=i
.
27. in CohenTannoudji et al.391
27
Time Dependent Perturbation Theory
We have used time independent perturbation theory to ﬁnd the energy shifts of states and to ﬁnd the change in energy eigenstates in the presence of a small perturbation. This material is covered in Gasiorowicz Chapter 21. The time dependent Schr¨dinger equations is o
h (H0 + V(t)) ck (t)e−iEk t/¯ φk k h ck (t)e−iEk t/¯ (Ek + V(t)) φk k h V(t)ck (t)e−iEk t/¯ φk k
= i¯ h
k
h ∂ck (t)e−iEk t/¯ φk ∂t
=
k
i¯ h
∂ck (t) h + Ek ck (t) e−iEk t/¯ φk ∂t
= i¯ h
k
∂ck (t) −iEk t/¯ h e φk ∂t
Now dot φn  into this equation to get the time dependence of one coeﬃcient. Such a perturbation can cause transitions between energy eigenstates. and brieﬂy in Griﬃths Chapter 9. V(t). Now we add a perturbation that depends on time.
h Vnk (t)ck (t)e−iEk t/¯ k
= =
i¯ h 1 i¯ h
∂cn (t) −iEn t/¯ h e ∂t
h Vnk (t)ck (t)ei(En −Ek )t/¯ k
∂cn (t) ∂t
Assume that at t = 0. We will calculate the rate of those transitions. Chapter XIII. o i¯ h ∂ψ(t) = (H0 + V(t)) ψ(t) ∂t
h h ck (t)φk e−iEk t/¯ with ck (t)e−iEk t/¯ = k
We will expand ψ in terms of the eigenfunctions: ψ(t) = φk ψ(t) . we are in an initial state ψ(t = 0) = φi and hence all the other ck are equal to zero: ck = δki .1
General Time Dependent Perturbations
Assume that we solve the unperturbed energy eigenvalue problem exactly: H0 φn = En φn . We will not consider the case of a perturbation that is time dependent. Our problem is now inherently time dependent so we go back to the time dependent Schr¨dinger equation.
If the ﬁrst order term is zero or higher accuracy is required. We will also use it as a basis to compute transition rates for the speciﬁc problem of harmonic potentials. if there is a large energy diﬀerence between the initial and ﬁnal states. We will ﬁnd that the perturbation will need frequency components compatible with ωni to cause transitions. This is not a limitation. all the ck (t) are small compared to ci (t) ≈= 1. We just put (1) the ﬁrst order ck (t) into the sum.3. the second order term can be computed. Again we are assuming t is small enough that ci has not changed much. ∂cn (t) ∂t ∂cn (t) ∂t ⎛ ⎞ 1 ⎝ (1) Vni (t)eiωni t + Vnk (t)ck (t)eiωnk t ⎠ i¯ h k=i ⎛ ⎞ t 1 ⎝ 1 iωnk t Vni (t)eiωni t + Vnk (t) e eiωki t Vki (t )dt ⎠ i¯ h i¯ h
k=i 0 t
=
=
c(2) (t) = n
−1 h ¯2
t
dt Vnk (t )eiωnk t
k=i 0 0
dt eiωki t Vki (t )
c(2) (t) n
−1 = 2 h ¯
t
t
dt Vnk (t )e
k=i 0
iωnk t 0
dt eiωki t Vki (t )
* See Example 27. then a transition to φn . ∂cn (t) ∂t
(1)
=
1 Vni (t)eiωni t i¯ h
t
c(1) (t) n
1 = i¯ h
0
eiωni t Vni (t )dt
This is the equation to use to compute transition probabilities for a general time dependent perturbation. We can deal with the decrease of the population of the initial state later. To ﬁrst order. Note that.*
. a transition can be made to an intermediate state φk . so the sum can be neglected. a slowly varying perturbation can average to zero.1: Transitions of a 1D harmonic oscillator in a transient E ﬁeld. In second order.392 Now we want to calculate transition rates.
V(r. If the initial and ﬁnal states have h energies such that this transition goes. For t → ∞. the time integral of the exponential gives (some kind of) delta function of energy conservation. As before. We will expend some eﬀort to determine exactly what delta function it is. h ω ω h ¯ω Ei = ωni En − Ei = h ¯ = En − Ei = En − ¯ ω h
This is energy conservation for the absorption of a quantum of energy ¯ ω. ω ω h ¯ω Ei = = = = −ωni En − Ei − h ¯ Ei − En En + hω ¯
This is energy conservation for the emission of a quantum of energy ¯ ω.393
27. With that factor. Lets take the case of radiation of an energy quantum ¯ ω.)
. (We can just use one of the exponentials at a time to make our formulas simpler. If one of the exponents is zero. the amplitude to be in the state φn will increase with time. We can make up any time dependence from a linear combination of sine and cosine waves. We deﬁne our perturbation carefully. To make an exponent zero we must have one of two conditions satisﬁed.2
Sinusoidal Perturbations
An important case is a pure sinusoidal oscillating (harmonic) perturbation. the absorption term is completely negligible. V depends on position but we don’t bother to write that for most of our calculations. Putting this perturbation into the expression for cn (t). we have V times a positive exponential plus a negative exponential. We can see the possibility of h absorption of radiation or of stimulated emission. we get
t
cn (t)
=
1 i¯ h
0
eiωni t Vni (t )dt
t
=
1 Vni i¯ h
0 t
dt eiωni t
eiωt + e−iωt
=
1 Vni i¯ h
0
dt
ei(ωni +ω)t + ei(ωni −ω)t
Note that the terms in the time integral will average to zero unless one of the exponents is nearly zero. t) = 2V (r) cos(ωt) → 2V cos(ωt) = V eiωt + e−iωt We have introduced the factor of 2 for later convenience.
If we tune the frequency just right we get inﬁnity otherwise we get zero. as is. for short times. If there is a free particle in the initial state or the ﬁnal state. satisﬁes this condition.394 The amplitude to be in state φn as a function of time is
t
cn (t)
=
1 Vni i¯ h
0
dt ei(ωni +ω)t ei(ωni +ω)t i(ωni + ω)
i(ωni +ω)t t =t
= = = = Pn (t) =
Vni i¯ h
t =0
−1 Vni e i¯ h i(ωni + ω) Vni i(ωni +ω)t/2 ei(ωni +ω)t/2 − e−i(ωni +ω)t/2 e i¯ h i(ωni + ω) Vni i(ωni +ω)t/2 2 sin ((ωni + ω)t/2) e i¯ h i(ωni + ω)
2 Vni 4 sin2 ((ωni + ω)t/2) (ωni + ω)2 h ¯2
In the last line above we have squared the amplitude to get the probability to be in the ﬁnal state. The transition rate is then given by
Γi→n ≡
2 2πVni dPn = δ(En − Ei + hω) ¯ dt h ¯
We would get a similar result for increasing E (absorbing energy) from the other exponential. This formula is what we need if either the initial or ﬁnal state is a continuum state. The frequency of the harmonic perturbation must be set so that ¯ ω is the energy h diﬀerence between initial and ﬁnal states. For long times (compared to ωni +ω which can be a VERY short time). we have a continuum state. Since the probability to be in the ﬁnal state increases linearly with time. The probability to be in state φn then is Pn (t) =
2 2 2 Vni 2πVni 2πVni δ(En − Ei + hω)t 2πt δ(ωni + ω) = δ(ωni + ω)t = ¯ h ¯ h ¯2 h ¯2
The probability to be in the ﬁnal state φn increases linearly with time. it is reasonable to describe this in terms of a transition rate. So. There is a delta function expressing energy conservation. the term in square brackets looks like some kind of delta function.1). We will show (See section 27.
. the absorption or emission of a particle. This is true both for the (stimulated) emission of a quantum of energy and for the absorption of a quantum. The 1 last formula is appropriate to use. Γi→n =
2 2πVni δ(En − Ei − ¯ ω) h h ¯
It does not make a lot of sense to use this equation with a delta function to calculate the transition rate from a discrete state to a discrete state. that the quantity in square brackets in the last equation is 2πtδ(ωni + ω).4.
t
cn (t)
=
1 i¯ h
0
eiωni t Vni (t )dt
T
c1
=
1 eE i¯ h eE i¯ h eE i¯ h
h ¯ 2mω
0 T
eiωt 1A + A† 0 dt
=
h ¯ 2mω
0
eiωt dt eiωt iω
T
=
h ¯ 2mω
0
eE h ¯ω eE = − h ¯ω eE = − h ¯ω = −
h ¯ eiωT − 1 2mω h ¯ iωT /2 iωT /2 − e−iωT /2 e e 2mω h ¯ iωT /2 e 2i sin(ωT /2) 2mω
.395 The above results are very close to a transition rate formula known as Fermi’s Golden Rule. We then have
Γi→f =
2 2πVni ρf (E) h ¯
where ρf (E) is the density of ﬁnal states. the ﬁnal state will be a continuum due to the continuum of states available to a free particle. The total rate to that continuum would be obtained by integrating over ﬁnal state energy. Imagine that instead of one ﬁnal state φn there are a continuum of ﬁnal states.3. We will need to carefully compute the density of those states. Calculate the probability to make a transition to the ﬁrst (and second) excited state.
27.1
Examples
Harmonic Oscillator in a Transient E Field
Assume we have an electron in a standard one dimensional harmonic oscillator of frequency ω in its ground state. h ¯ (A + A† ) V = eE 2mω We now use our time dependent perturbation result to compute the transition probability to the ﬁrst excited state. often known as phase space. We can write this in terms of the raising an lowering operators.3
27. an integral done simply with the delta function. When particles (like photons or electrons) are emitted. The perturbation is eEx for 0 < t < T and zero for other times. An weak electric ﬁeld is applied for a time interval T .
We do see that the transition probability oscillates with the time during which the E ﬁeld is applied.396 h e2 E 2 ¯ 2 2 2 2mω 4 sin (ωT /2) h ¯ ω 2e2 E 2 sin2 (ωT /2) m¯ ω 3 h
P1 P1
= =
As long as the E ﬁeld is weak. Its not too bad to do since there is only one intermediate state.1
Derivations and Computations
The Delta Function of Energy Conservation
For harmonic perturbations. (Note that we have divided our function to be investigated by t2 . 4 sin2 ((ωni + ω)t/2) Pn ∝ (ωni + ω)2 For simplicity of analysis lets consider the characteristics of the function g(Δ ≡ ωni + ω) = 4 sin2 ((ωni + ω)t/2) 4 sin2 (Δt/2) ≡ 2 t2 (ωni + ω) Δ2 t2
1 for values of t >> Δ . g(Δ) = 1 while for all other values for Δ.
∞ ∞
dΔ f (Δ)g(Δ) =
−∞
f (Δ = 0)
−∞ ∞
dΔ g(Δ) 4 sin2 (Δt/2) Δ2 t2 4 sin2 (y) 4y 2 sin2 (y) y2
=
f (Δ = 0)
−∞ ∞
dΔ
=
f (Δ = 0)
−∞
dΔ 2 t
∞
=
f (Δ = 0)
dy
−∞
.4
27.
To ﬁnd out exactly what delta function it is. We would get a (much) larger transition probability if we applied an oscillating E ﬁeld tuned to have the right frequency to drive the transition. This is clearly some form of a delta function. g(Δ) approaches zero for large t. If we really want to compute this.
27. Clearly the probability to make a transition to the second excited state is zero in ﬁrst order. For Δ = 0. This is a second order calculation.4. the initial state will not be signiﬁcantly depleted and the assumption we have made concerning that is valid. we have derived a probability to be in the ﬁnal state φn proportional to the following. we can use our ﬁrst order result for c1 and calculate the transition probability to the n = 2 state from that. we need to integrate over Δ.
What z components of orbital angular momentum are allowed in the 2P states generated by this transition? 2. You need not evaluate the radial part of the integral. Assume we have an electron in a standard one dimensional harmonic oscillator of frequency ω in its ground state. A hydrogen atom is placed in an electric ﬁeld which is uniform in space and turns on at t = 0 then decays exponentially.5
Homework Problems
1.
The deﬁnite integral over y just gives π (consult your table
dΔ f (Δ)g(Δ) =
−∞
f (Δ = 0) 2π δ(Δ) t
2π t
g(Δ) = 4 sin2 ((ωni + ω)t/2) (ωni + ω)2 Q. You will need to calculate to second order.397
∞
=
2 f (Δ = 0) t
dy
−∞
sin2 (y) y2
We have made the substitution that y = of integrals). Now calculate the probability to make a transition to the second excited state. That is.
∞
Δt 2 .D. =
2πt δ(ωni + ω)
27.6
Sample Test Problems
1. It is subjected to the additional potential W = −eξx for a a time interval τ . What is the probability that. A one dimensional harmonic oscillator is in its ground state.E. the hydrogen atom has made a transition to the 2p state? 2. The atom is initially in its ground state. An weak electric ﬁeld is applied for a time interval T .
. as t → ∞. Calculate the probability to make a transition to the ﬁrst excited state. E(t) = E0 e−t/τ . so the result is simple. Calculate the probability to make a transition to the ﬁrst excited state (in ﬁrst order). E(t) = 0 for t < 0 and E(t) = E0 e−γt for t > 0. Find the probability for the atom to have made a transition to the 2P state as t → ∞.
27. A hydrogen atom is in a uniform electric ﬁeld in the z direction which turns on abruptly at t = 0 and decays exponentially as a function of time.
So far. Chapter XIII. Planck was also correctly counting this inﬁnite number of states to get the correct Black Body formula. directions of propagation. Notice that the emission of a quantum of radiation with energy of ¯ ω is like the raising of a Harmonic h Oscillator state. (In fact.
Lets assume that there is some ElectroMagnetic ﬁeld around the atom. We now have the solution of the Harmonic Oscillator problem using operator methods. We need to quantize the EM ﬁeld into photons satisfying Planck’s original hypothesis. Similarly the absorption of a quantum of radiation is like the lowering of a HO state. and brieﬂy in Griﬃths Chapter 9. setting the boundary conditions.1) is given by H= e 1 p+ A 2m c
2
+ V (r). in our treatment of atoms. and arbitrary ﬁeld would be a linear combination of many frequencies.1
The Photon Field in the Quantum Hamiltonian
The Hamiltonian for a charged particle in an ElectroMagnetic ﬁeld (See Section 19. Planck was already integrating over an inﬁnite number of photon (like HO) states. He did it by considering a cavity with some volume.398
28
Radiation in Atoms
Now we will go all the way back to Planck who proposed that the emission of radiation be in quanta with E = hω to solve the problem of Black Body Radiation.
28. e V= A·p mc Lets also assume that the ﬁeld has some frequency ω and corresponding wave vector k. in CohenTannoudji et al. The Hamiltonian then becomes i H≈ p2 e + A · p + V (r). and polarizations. This material is covered in Gasiorowicz Chapter 22. The ﬁeld is not extremely strong so that the A2 term can be neglected (for our purposes) and we will work in the ¯ Coulomb gauge for which p · A = h ∇ · A = 0. the same integral we would do if we had an inﬁnite number of Harmonic Oscillator states. 2m mc
Now we have a potentially time dependent perturbation that may drive transitions between the atomic states. This is really the realm of Quantum Electrodynamics. we ¯ have not included the possibility to emit or absorb real photons nor have we worried about the fact that Electric and Magnetic ﬁelds are made up of virtual photons. but we do have the tools to understand what happens as we quantize the EM ﬁeld. E = hω. then letting the volume go to inﬁnity.) A(r. Lets ¯ start by writing A in terms of the number of photons in the ﬁeld (at frequency ω and wave
. t) ≡ 2A0 cos(k · r − ωt) where A0 is a real vector and we have again introduced the factor of 2 for convenience of splitting the cosine into two exponentials.
and the hence the perturbing ﬁeld is never really zero. We now want to go from a classical harmonic oscillator to a quantum oscillator. But what about decays of atoms with no applied ﬁeld? Here we need to go beyond our classical E&M calculation and quantize the ﬁeld. With this change. our perturbation becomes A(r.14. There are terms with both negative and positive ω so that we expect to see both stimulated emission of quanta and absorption of quanta in the the presence of a time dependent EM ﬁeld.. This factor will be canceled when we correctly compute the density of ﬁnal states. Of course we have this for all frequencies.) of light. one for each wave vector (or frequency. Also note that our perturbation still depends on the volume we assume. in which the ground state energy is not zero. Using classical E&M to compute the energy in a ﬁeld (See Section 28. not just the one we have been assuming without justiﬁcation. Now there is a perturbation even with no applied ﬁeld (N = 0).
VN =0 = VN =0 e
iωt
e 2π¯ c2 h e A·p = = mc mc ωV
1 2
e−i(k·r−ωt) ˆ · p
We can plug this right into our expression for the decay rate (removing the eiωt into the delta function as was done when we considered a general sinusoidal time dependent perturbation). Since the terms in the perturbation above emit or absorb a photon. and the photon has energy ¯ ω. t) =
2π¯ c2 N h ωV 2π¯ c2 N h ωV
ˆ 2 cos(k · r − ωt) ˆ ei(k·r−ωt) + e−i(k·r−ωt)
1 2
We have introduced the unit vector ˆ to give the direction (or polarization) of the vector potential. We view A as an operator which either creates or absorbs a photon.
. We do this by changing N to N + 1 in the term that creates a photon in analogy to the raising operator A† in the HO. h 2πc2
We may then turn this around and write A in terms of the number of photons N . A0 2 = N ¯ω h 2π¯ c2 N h 2πc2 = 2V ω ωV
1 2
A(r. lets assume the number of photons in the ﬁeld is the n of a h harmonic oscillator. t) = 2π¯ c2 h ωV
1 2
ˆ
√ i(k·r−ωt) √ Ne + N + 1e−i(k·r−ωt)
Remember that one exponential corresponds to the emission of a photon and the other corresponds to the the absorption of a photon. Essentially. raising or lowering the harmonic oscillator in the vacuum. we are postulating that the vacuum contains an inﬁnite number of harmonic oscillators. We now have a perturbation that may induce radiative transitions.399
vector k). It has the right steps in energy. we ﬁnd that the energy inside a volume V is Energy = ω2 V A0 2 = N ¯ ω.1) represented by a vector potential A(r. t) = A(r. t) = 2A0 cos(k · r − ωt)..
¯ h ¯
The delta function reminds us that we will have to integrate over ﬁnal states to get a sensible answer. When we quantize these oscillators.2
Decay Rates for the Emission of Photons
Our expression for the decay rate of an initial state φi into some particular ﬁnal state φn is Γi→n =
2 2πVni δ(En − Ei + hω). We will integrate over photon energies and directions.
28. We will sum over photon polarizations.
28. we have the matrix element of the perturbing potential. Taking out the harmonic time dependence (to the delta function) as before. (Remember ω = kc for light. The states are distinguishable so we add the decay rates. Vni h e e 2π¯ c2 A · pφi = = φn  mc mc ωV
1 2
φn e−ik·r ˆ · pφi
We just put these together to get Γi→n Γi→n = = 2π¯ c2 h 2π e2 ¯  φn e−ik·r ˆ · pφi 2 δ(En − Ei + hω) h ¯ m 2 c2 ωV (2π)2 e2  φn e−ik·r ˆ · pφi 2 δ(En − Ei + hω) ¯ m2 ωV
We must sum (or integrate) over ﬁnal states. we can correctly compute the EM transition rates in atoms. the vacuum has a ground state energy density in the EM ﬁeld (equivalent to half a photon of each type). We have not yet written the quantum equations that the EM ﬁeld must satisfy. not the amplitudes.400 We have taken a step toward quantization of the EM ﬁeld. With this step. Note that we have postulated that the vacuum has an inﬁnite number of oscillators corresponding to the diﬀerent possible modes of EM waves.1). The PBC are equivalent to this but allow
. That vacuum EM ﬁeld is then responsible for the spontaneous decay of excited states of atoms through the emission of a photon. at least when we emit or absorb a photon. we proceed to include the matrix element of the perturbing potential. Nevertheless.) We will assume for the sake of calculation that the photons are conﬁned to a cubic volume in position space of V = L3 and impose periodic boundary conditions on our ﬁelds. Now we wish to know how many photon states are in a region of phase space centered on the wave vector k with (small) volume in kspace of d3 k. For the box we had boundary conditions that the wavefunction go to zero at the wall of the box. We will sum over the ﬁnal atomic states when that is applicable.3
Phase Space: The Density of Final States
We have some experience with calculating the number of states for fermions in a 3D box (See Section 12. All of this is quite doable. (Really we could require the ﬁelds to be zero on the boundaries of the box by choosing a sine wave. Our ﬁrst step is to understand the number of states of photons as Planck (and even Rayleigh) did to get the Black Body formulas.1. with the aid of the delta function. although they are closely related to Maxwell’s equations.
so they must vary inside the integral. We will use this phase space formula for decays of atoms emitting a photon. we may also need to sum over ﬁnal states of the atom. A quick estimate of the decay rate of an atom (See Section 28.4
Total Decay Rate Using Phase Space
Now we are ready to sum over ﬁnal (photon) states to get the total transition rate.) Our ﬁnal result.
V d3 k Γi→n = (2π)3
pol. its momentum is ﬁxed due to momentum conservation. (In fact. The two polarizations are transverse to the photon direction. Γtot =
k.401 us to deal with single exponentials instead of real functions.
.3) gives τ ≈ 50 psec. kx L = 2πnx ky L = 2πny kz L = 2πnz d3 n = dnx = dny = dnz =
L 2π dkx L 2π dky L 2π dkz
L3 3 (2π)3 d k
=
V 3 (2π)3 d k
That was easy.14. however.
V d3 p Γi→n (2π¯ )3 h
=
λ
V d3 p (2π)2 e2  φn e−ik·r ˆ(λ) · pe φi 2 δ(En − Ei + hω) ¯ (2π¯ )3 m2 ωV h d3 p  φn e−ik·r ˆ(λ) · pe φi 2 δ(En − Ei + hω) ¯ ω h h p2 d(¯ ω)dΩγ ¯  φn e−ik·r ˆ(λ) · pe φi 2 δ(En − Ei + hω) ¯ pc c ¯ pd(¯ ω)dΩγ  φn e−ik·r ˆ(λ) · pe φi 2 δ(En − Ei + hω) h
λ
= = = =
e2 2π¯ 3 m2 h e2 2π¯ 3 m2 h
λ
λ
e2 2 2 2 2π¯ m c h e2 2π¯ 2 m2 c2 h
λ
Ei − En dΩγ  φn e−ik·r ˆ(λ) · pe φi 2 c
Γtot =
e2 (Ei − En ) 2π¯ 2 m2 c3 h
dΩγ  φn e−ik·r ˆ(λ) · pe φi 2
λ
This is the general formula for the decay rate emitting one photon.14. the atom recoils in the ﬁnal state. will be independent of volume so we can let the volume go to inﬁnity.)
28. even our simple case. we will label the electron’s momentum to avoid confusion.pol
Γi→n →
pol. Depending on the problem. Since both the momentum of the photon and the electron show up in this equation. A more general phase space formula (See Section 28.2) based on our calculation can be used with more than one free particle in the ﬁnal state. the decay rate.
5
Electric Dipole Approximation and Selection Rules
We can now expand the e−ik·r ≈ 1 − ik · r + .. Γtot = e2 (Ei − En ) 2π¯ 2 m2 c3 h dΩγ  φn e−ik·r ˆ(λ) · pe φi 2
λ
.
∞
φn ˆ · rφi
=
0 ∞
∗ r2 drRnn n Rni
i
dΩY ∗ mn ˆ · rY n ˆ dΩY ∗ mn ˆ · r Y n
z
i mi
=
0
∗ r3 drRnn n Rni x sin θ cos φ
i
i mi
ˆ· r = ˆ = φn ˆ · rφi =
+ +
y
sin θ sin φ +
x
cos θ
x
4π 3 4π 3
∞
z Y10
−
+i √ 2
i
y
Y11 +
+i √ 2
y
Y1−1 + −
x
∗ r3 drRnn n Rni 0
dΩY ∗ mn n
z Y10
+i √ 2
y
Y11 +
x
+i √ 2
y
Y1−1 Y
i mi
At this point. The dominant decays will be those from the zeroth order approximation which is e−ik·r ≈ 1. lets bring all the terms in the formula back together so we know what we are doing. r] = 0. Since k · r ≈ α and the matrix element is squared. ≈ = = = ˆ · φn pe φi im ˆ · φn [H. We can proceed further. r] = and we can write p =
im h [H. with the angular part of the (matrix element) integral.. we can make general progress on computation of the matrix element. term to allow us to compute matrix elements more easily. our expansion will be in powers of α2 which is a small 2 number. In this Electric Dipole approximation. r]φi h ¯ im (En − Ei )ˆ · φn rφi h ¯ im(En − Ei ) φn ˆ · rφi h ¯
φn e−ik·r ˆ · pe φi
This equation indicates the origin of the name Electric Dipole: the matrix element is of the vector r which is a dipole. then [H. r] ¯
h ¯ p im
in terms of the commutator. This is called the Electric dipole approximation.402
28. p2 If the Hamiltonian is of the form H = 2m + V and [V.
The integral with three spherical harmonics in each term looks a bit diﬃcult.) The general formula for rewriting the product of two spherical harmonics (which are functions of the same coordinates) is
1+ 2
Y
1 m1 (θ. but. φ)
.
Γtot =
3 αωin 2πc2
dΩγ  φn ˆ · rφi 2
λ
We proceed with the calculation to ﬁnd the E1 selection rules. φ)
=
= i −1
3(2 i + 1) 0 i 100 4π(2 + 1)
(m + mi ) i 1mi m Y
(mi +m) (θ. φ)Y
i mi
(θ. φ)
The square root and 0 1 2 00 can be thought of as a normalization constant in an otherwise normal ClebschGordan series. We will write the product of two spherical harmonics in terms of a sum of spherical harmonics. Its very similar to adding the angular momentum from the two Y s.
i +1
Y1m (θ. the coordinates of particle one and of particle two. φ)Y
2 m2 (θ.) (The derivation of the above equation involves a somewhat detailed study of the properties of rotation matrices and would take us pretty far oﬀ the current track (See Merzbacher page 396). =
3 αωin 2πc2 3 αωin 2πc2
dΩγ
λ
4π 3 4π 3
φn
∞
z Y10
+
−
x
+i √ 2
y
Y11 +
x
+i √ 2
2 y
Y1−1 φi
2
=
dΩγ
λ
r
0
3
∗ drRnn
n
Rni
i
dΩY
∗
n mn
z Y10
+
−
x
+i √ 2
y
Y11 +
x
+i √ 2
y
Y1−1 Y
i mi
We will attempt to clearly separate the terms due to φn ˆ · rφi for the sake of modularity of the calculation. φ) =
(2
2
1
=
1−
+ 1)(2 2 + 1) 0 4π(2 + 1)
1 2 00
(m1 +m2 )
1 2 m1 m2
Y
(m1 +m2 ) (θ. with the usual notation for the ClebschGordan coeﬃcients n mn  i 1mi m . we can use a ClebschGordan series like the one in addition of angular momentum to help us solve the problem.403 e2 (Ei − En ) 2π¯ 2 m2 c3 h
3 αωin 2πc2
= =
dΩγ
λ
im(En − Ei ) φn ˆ · rφi h ¯
2
dΩγ  φn ˆ · rφi 2
λ
This is a useful version of the total decay rate formula to remember. a case we will work out below for transitions to s states.) First add the angular momentum from the initial state (Y i mi ) and the photon (Y1m ) using the ClebschGordan series. (Note that things will be very simple if either the initial or the ﬁnal state have = 0. (Note that the normal addition of the orbital angular momenta of two particles would have product states of two spherical harmonics in diﬀerent coordinates. Its the same series as we had for addition of angular momentum (up to a constant).
it is a small eﬀect compared to the Electric Dipole term. The above selection rules apply only for the Electric Dipole (E1) approximation. We can also easily note that we have no operators which can change the spin here. Higher order terms in the expansion. since the photon is spin 1. that adding angular momentum 1 to 1 can only give answers in the range  1 − 1 < n < 1 + 1 so the change in in between the initial and ﬁnal state can only be Δ = 0. There is one absolute selection rule coming from angular momentum conservation. like the Electric Quadrupole (E2) or the Magnetic Dipole (M1). We actually haven’t yet included the interaction between the spin and the ﬁeld in our calculation. lets write out the decay rate formula. allow other decays but the rates are down by a factor of α2 or more.
. For other values. all the ClebschGordan coeﬃcients above will be zero. ±1.404
dΩY ∗ mn Y1m Y n
i mi
=
3(2 i + 1) 4π(2 n + 1)
n 0 i 100
n mn  i 1mi m
dΩY ∗ mn n =
z Y10
+
−
x
+i √ 2
y
Y11 +
x
+i √ 2
y
Y1−1 Y +
i mi
3(2 i + 1) 4π(2 n + 1)
n 0 i 100
z
n mn  i 1mi 0
−
x
+i √ 2
y
n mn  i 1mi 1
+
x
+i √ 2
y
n mn  i 1mi
−1
I remind you that the ClebschGordan coeﬃcients in these equations are just numbers which are less than one. but. from the addition of angular momentum. therefore Δ = ±1. We also know from the addition of angular momentum that the z components just add like integers. No j = 0 to j = 0 transitions in any order of approximation. The equation we derive can be used to give us a great deal of information. As a summary of our calculations in the Electric Dipole approximation. They can often be shown to be zero if the angular momentum doesn’t add up. We also know that the Y1m are odd under parity so the other two spherical harmonics must have opposite parity to each other implying that n = i . φn ˆ · rφi = (2 i + 1) (2 n + 1)
z ∞ n 0 i 100 0 n mn  i 1mi 0 ∗ r3 drRnn n Rni
i
+
−
x
+i √ 2
y
n mn  i 1mi 1
+
x
+i √ 2
y
n mn  i 1mi
−1
We know. so the three ClebschGordan coeﬃcients allow Δm = 0. ±1. So certainly Δs = 0.
1 3 dΩ
mi
Y ∗ mn n
z Y10 +
−
x
+i √ 2
y
Y11 +
x
+i √ 2
2 y
Y1−1 Y
i mi
. the number of diﬀerent mi allowed.
3 αωin = 2πc2
Γtot
dΩγ
λ
4π 3
∞
2
r
0
3
∗ drRnn
n
Rni
i
dΩY
∗
n mn
z Y10
+
−
x
+i √ 2
y
Y11 +
x
+i √ 2
y
Y1−1 Y
i mi
we specialize to the 2p to 1s decay. dΩ
∗ Y00 z Y10
+
= = dΩ
∗ Y00
1 √ 4π 1 √ 4π
+i y √ Y1−1 Y1mi 2 − x+i y x+i y √ dΩ z Y10 + Y11 + √ Y1−1 Y1mi 2 2 − x+i y x+i y √ δmi (−1) + √ δ mi 1 z δ mi 0 + 2 2
x y
−
+i √ 2
Y11 +
x
z Y10 +
=
1 4π
+i +i √ y Y11 + x √ y Y1−1 Y1mi 2 2 1 2 2 2 z δmi 0 + ( x + y )(δmi (−1) + δmi 1 ) 2
x
−
2
Lets assume the initial state is unpolarized.
3 αωin = 2πc2
Γtot
dΩγ
λ
4π 3
∞
2
r
0
3
∗ drR10 R21
∗ dΩY00
z Y10
+
−
x
+i √ 2
y
Y11 +
x
+i √ 2
y
Y1−1 Y1mi
perform the radial integration.
∞ ∗ r3 drR10 R21 0 ∞
=
0
r3 dr 2 1 √ 6 1 √ 6 1 a0 1 a0
5 4
1 a0
∞
3 2
e−r/a0
1 √ 24
1 a0
5 2
re−r/2a0
=
r4 dre−3r/2a0
0
4
=
2a0 3
5
∞
x4 dxe−x
0
= =
2 1 √ 6 3 √ 2 4 6 3
a0 (4!)
5
a0
and perform the angular integration.405
28. so we will sum over mi and divide by 3.6
Explicit 2p to 1s Decay Rate
Starting from the summary equation for electric dipole transitions. above.
The integral over photon direction clearly just gives a factor of 4π since there is no direction dependence left in the integrand (due to our assumption of an unpolarized initial state). integrate over photon directions. Lets assume that we are not interested in measuring the photon’s polarization. and (eventually) sum over the diﬀerent mn of the ﬁnal state atoms. The polarization vector is constrained to be perpendicular to the photons direction ˆ · kp = 0 so there are two linearly independent polarizations to sum over.7
General Unpolarized Initial State
If we are just interested in the total decay rate. we can go further. but. Γtot =
3 √ 2αωin (2)(4π) 4 6 2 3c
2 3
5
2
a0
3 4αωin √ 1 4 6 = 2 12π 9c
2 3
5
2
a0
28. we must still sum over photon polarization. This just introduces a factor of two as we sum over ﬁnal polarization states. Usually we only want the total decay rate to some ﬁnal state so we sum over polarizations of the photon. Γtot Γtot Γtot Γtot = = = =
3 αωin 2πc2 3 αωin 2πc2 3 αωin 2πc2 3 αωin 2πc2
dΩγ  φn ˆ · rφi 2
λ
dΩγ  φn rφi · ˆ2
λ
dΩγ rni · ˆ2
λ
dΩγ rni 2 cos2 Θ
λ
Where Θ is the angle between the matrix element of the position vector rni and the polarization vector ˆ. The decay rate should not depend on the polarization of the initial state.
. We begin with a simple version of the total decay rate formula in the E1 approximation.406 1 1 4π 3 1 12π 1 12π 1 12π 1 + ( 2
= = = =
2 z δ mi 0 mi 2 z 2 z
2 x
+
2 y )(δmi (−1)
+ δ mi 1 )
1 + ( 2
2 x
2 x
+
2 y
2 y )(1
+ 1)
+
+
Our result is independent of photon polarization since we assumed the initial state was unpolarized. It is far easier to understand the sum over polarizations in terms of familiar vectors in 3space than by using sums of ClebschGordan coeﬃcients. based on the rotational symmetry of our theory.
It is then easy to see that cos Θ1 cos Θ2 = = sin θ cos φ sin θ sin φ
The sum of cos2 Θ over the two polarizations then just gives sin2 θ. ˆ ˆ(1) × ˆ(2) = k The ﬁgure below shows the angles.407 Lets pick two transverse polarization vectors (to sum over) that form a right handed system with the direction of photon propagation. and the ˆ(1) direction as what is usually called the xaxis. Therefore the decay rate becomes Γtot Γtot Γtot Γtot = = = =
3 αωin 2πc2
dΩγ rni 2 cos2 Θ
λ
3 αωin rni 2 dΩγ sin2 θ 2πc2 3 αωin rni 2 2π d(cos θ) sin2 θ 2πc2 3 αωin rni 2 2π 2πc2 1
d(cos θ)(1 − cos2 θ)θ
−1
.
k
θ
r ni
Θ2 Θ1
ε2
ϕ
ε1
The projection of the vector rni into the transverse plan gives a factor of sin θ. basically picking the photon direction as the polar axis.
For the case of a transition in a single electron atom ψn m → ψn m + γ. summed over m .
Γtot =
3 4αωin rni 2 3c2
We still need to sum over the ﬁnal atomic states as necessary. summed over photon polarizations and integrated over photon direction.
. We must choose the case and = 1.
3 4αωin = 3c2 2 + 1 ∞ ∗ R10 R21 r3 0 2 3 4αωin = 9c2 ∞ ∗ R10 R21 r3 0 2
= −1
Γtot
dr
dr
This is the same result we got in the explicit calculation.
Γtot
3 4αωin = 2 3c
+1 2 +1 2 +1
∞ ∗ Rn 0
2
Rn r dr
3
for
=
+1 −1
The result is independent of m as we would expect from rotational symmetry. second edition. page 467). lets recompute the 2p to 1s decay rate for hydrogen. As a simple check.408
1
Γtot
=
3 αωin rni 2 2π 2πc2 3 αωin rni 2 2π 2πc2 3 αωin rni 2 2π 2πc2
dx(1 − x2 ) x− 2− x3 3 2 3
1 −1
−1
Γtot Γtot Γtot Γtot
= = = =
3 8π αωin rni 2 2πc2 3 3 4αωin rni 2 3c2
This is now a very nice and simple result for the total decay rate of a state. the properties of the ClebschGordan coeﬃcients can be used to show (See Merzbacher.
assume that φ = 0 and the photon is therefore emitted in the xz plane. The basic reason for this is that all vectors transform the same way under rotations. This will be true for any vector operator. One transverse polarization can be in the y direction.
z
term remains and the rate is proportional to
2 z. We then look at our result for the angular integration in the matrix element
∗ dΩY00 z Y10
+
−
x
+i √ 2
y
Y11 +
2 x
x
+i √ 2
2 y
Y1−1 Y1mi + δ mi 1 )
2 x
=
1 4π
2 z δ mi 0
1 + ( 2
+
2 y )(δmi (−1)
=
1 4π
1 ( 2
+
2 y)
where we have set mi = 1 eliminating two terms. The rate will be independent of the azimuthal angle. because the vector operator is very much like adding an additional = 1 to the initial state angular momentum. The x component is proportional to cos θγ . We have seen in the sections on the Electric Dipole approximation and subsequent calculations that the vector operator r could be written as its magnitude r and the spherical harmonics Y1m . Lets study the rate as a function of the angle of the photon from the z axis. and ClebschGordan coeﬃcients. so all have the same angular properties.409
28. We see that the rate is proportional to 2 + 2 . θγ . We found that the Y1m could change the orbital angular momentum (from initial to ﬁnal state) by zero or one unit. Note that it makes sense to write a vector V in terms of the spherical harmonics using V± = ∓ Vx ± iVy √ 2
.
The angular
28.8
Angular Distributions
We may also deduce the angular distribution of photons from our calculation. We had the equation for the decay rate.
3 αωin = 2πc2
Γtot
dΩγ
λ
4π 3
∞
2
r
0
3
∗ drR10 R21
∗ dΩY00
z Y10
+
−
x
+i √ 2
y
Y11 +
x
+i √ 2
y
Y1−1 Y1mi
We have performed that radial integration which will be unchanged. Wigner and Eckart proved that all matrix elements of vector operators can be written as a reduced matrix element which does not depend on any of the m.9
Vector Operators and the Wigner Eckart Theorem
There are some general features that we can derive about operators which are vectors. x y If we assume that mi = 0 then only the distribution then goes like sin2 θγ . The other is in the xz plane perpendicular to the direction of the photon. We still must sum x y over the two independent transverse polarizations. Assume that we start in a polarized state with mi = 1. In fact. being written in terms of the Y1m . Lets take the 2p to 1s calculation as an example. operators that transform like a vector under rotations. So the rate is proportional to 2 + 2 = 1 + cos2 θγ . that is. For clarity.
all the angular part is the same. Nevertheless. dPi dt = −Γtot
t=0
For larger times we can assume that the probability to make a transition away from the initial state is proportional to the probability to be in the initial state.
28. dPi (t) = −Γtot Pi (t) dt The solution to this simple ﬁrst order diﬀerential equation is Pi (t) = Pi (t = 0)e−Γtot t If you are having any trouble buying this calculation. The WignerEckart theorem says α j m V q αjm = j m j1mq α j V αj Here α represents all the (other) quantum numbers of the state. 0. The theorem can be generalized for spherical tensors of higher (or even lower) rank than a vector. Γtot =
n
Γi→n
This transition rate is the probability per unit time to make a transition away from the initial state evaluated at t = 0. α j V αj is a reduced matrix element. Lets consider our vector V q where the integer q runs from 1 to +1. we have assumed that our calculations need only be valid near t = 0. This theorem again allows us to deduce that Δ = −1. Writing this as an equation we have. not the angular momentum quantum numbers.410 and V0 = Vz . (Its easy to understand that if we take a matrix element of 10r it will be 10 times the matrix element of r.10
Exponential Decay
We have computed transition rates using our theory of radiation. We have already done this for angular momentum operators. + 1. More speciﬁcally. This theorem states that all vectors have essentially the same angular behavior. we have assumed that we start out in some initial state i and that the amplitude to be in that initial state is one. Assume we have computed the total transition rate. Its the same for all values of m and q.
. jm represent the usual angular momentum quantum numbers of the states. think of a large ensemble of hydrogen atoms prepared to be in the 2p state at t = 0. The probability to be in the initial state will become depleted for times on the order of the lifetime of the state. We can account for this in terms of the probability to remain in the initial state. In doing this. Clearly the number of atoms remaining in the 2p state will obey the equation dN2p (t) = −Γtot N2p (t) dt and we will have our exponential time distribution.
. this lifetime can be very short. It can be characterized by its Full Width at Half Maximum (FWHM) of Γ.411 We may deﬁne the lifetime of a state to the the time after which only τ= 1 Γtot
1 e
of the decaying state remains. ¯ Ii (ω) = φi (ω)2 = 1 (ω − ω0 )2 +
Γ2 4
This gives the energy distribution of an unstable state. We know that energy conservation can be violated for short times according to the uncertainty principle h ¯ ΔEΔt ≤ . It is called the BreitWigner line shape. 2
We may be more quantitative.11
Lifetime and Line Width
Now we have computed the lifetime of a state. nuclear.
∞
φi (ω)
∝
0 ∞
ψi (t)eiωt dt
∝
0 ∞
h e−iEi t/¯ e−Γt/2 eiωt dt
=
0 ∞
e−iω0 t e−Γt/2 eiωt dt
=
0
ei(ω−ω0 +i 2 )t dt 1 Γ ei(ω−ω0 +i 2 )t Γ i(ω − ω0 + i 2 ) i (ω − ω0 + i Γ ) 2
∞
Γ
= =
0
We may square this to get the probability or intensity as a function of ω (and hence E = hω). For some atomic. or particle states. then we have ψi (t)2 = e−Γt ψi (t) ∝ e−Γt/2
h ψi (t) ∝ e−iEi t/¯ e−Γt/2
We may take the Fourier transform of this time function to the the amplitude as a function of frequency.
28. If the probability to be in the initial state is proportional to e−Γt . 2 This means that a unstable state can have an energy width on the order of ΔE ≈ h ¯ Γtot .
For the 2p to 1s transition in hydrogen. like those from E2 or M1 will be relatively narrower.6 × 109 per second. It also depends on temperature. Weaker transitions. • Doppler broadening.1
Other Phenomena Inﬂuencing Line Width
We have calculated the line shape due to the ﬁnite lifetime of a state.11. ΔE = hΓ = ¯ (1. An atom or molecule moving through a gas sweeps through a volume per second proportional to its cross section σ and velocity. and it usually is.4 × 10−6 eV 1.412 The BreitWigner will be the observed line shape as long as the density of ﬁnal states is nearly constant over the width of the line. If this is true. These are: • Collision broadening.
28. Collision broadening occurs when excited atoms or molecules have a large probability to change state when they collide with other atoms or molecules. allowing use in precision systems. can play a role in the observed line width. we’ve calculated a decay rate of 0. This is basically a quantum mechanical eﬀect broadening a state because the state only exists for a short period of time. other phenomena. the width is about 10−7 of the photon energy.602 × 10−12 erg/eV
Since the energy of the photon is about 10 eV. As Γ → 0 this line shape approaches a delta function. Its narrow but not enough for example make an atomic clock.6 × 109 sec−1 ) ≈ 0. If the mean time between collisions is less than the lifetime.05 × 10−27 erg sec)(0. δ(ω − ω0 ). the mean time to collision is an important consideration when we are assessing the lifetime of a state. both of a quantum and nonquantum nature. then the linewidth will be dominated by collision broadening. If we attempt to measure line widths. We can estimate the velocity from the temperature.
. The number of collisions it will have per second is then Γc = Ncollision/sec = nvσ where n is the number density of molecules to collide with per unit volume. 1 3 mv 2 = kT 2 2 3kT vRMS = m 3kT σ Γc = n m The width due to collision broadening increases with he pressure of the gas. We can compute the FWHM of the width of the photon line. and • Recoil.
we should be aware of the eﬀect of recoil. In fact. An analysis shows that the probability is approximately h P0 = e−Erecoil /¯ ωHO Thus a large fraction of the radiation is emitted (and reabsorbed) without a large energy shift. Basically. One example of this would be to measure the gravitational red (blue) shift of xrays. Lets do the calculation for Hydrogen.
28. (Remember that the crystal may have 1023 atoms in it and that is a large number. the atom emitting an xray is in a harmonic oscillator (ground) state bound to the rest of the crystal.1
Phenomena of Radiation Theory
The M¨ssbauer Eﬀect o
In the case of the emission of xrays from atoms. One can see that the eﬀect of recoil becomes more important as the energy radiated increases. We know that the frequency of photons is shifted if the source is moving – shifted higher if the source is moving toward the detector. making the energy shift very small. This has the consequence that a photon emitted by an atom will not have the right energy to be absorbed by another atom.12
28. the whole crystal. The same recoil eﬀect shifts the energy need to excite a state upward. or o at least a large part of it may recoil.12. this is about 10 eV over 1860 MeV. The photon energy is shifted downward compared to the energy diﬀerence between initial and ﬁnal atomic states.413 Doppler broadening is a simple nonquantum eﬀect. M¨ssbauer discovered that atoms in a crystal need not recoil signiﬁcantly. The energy shift due to recoil is more signiﬁcant for nuclear decays. still the energy shift due to recoil can be bigger than the natural line width of a state. Because the atom is heavy. One could move the detector at diﬀerent velocities to ﬁnd out when reabsorption was maximum and thus make a very accurate measurement of energy shifts. it can carry a great deal of momentum while taking little energy. Δω = Δω = ω kT /m = c v ω c kT mc2
This becomes important when the temperature is high. For some experiments it is useful to be able to measure the energy of the xray by reabsorbing it. the recoil of the atom will shift the energy of the xray so that it is not reabsorbed. there is a good chance the HO remains in the ground state. or less than one part in 108 . pH = pγ E pγ ≈ c p2 E2 = = 2mp 2mp c2 E ΔE = E 2mp c2
EH
For our 2p to 1s decay in Hydrogen. When the xray is emitted. and shifted lower if it is moving away. raising it up to the same excited state that decayed. Finally. When an atom emits a photon.
. the atom must recoil to conserve momentum.
The red shift was o compensated by moving a detector. This optical pumping to achieve a population inversion can be done in a number of ways. The Neon decays more quickly so its deexcitation is dominated by photon emission. the emission from one atom will increase the emission rate from the other atoms and that emission will stimulate more. putting the Neon in a highly excited state.
1 2
A(r. If the population of the excited state can be continuously pumped up.2
LASERs
Light Ampliﬁcation through Stimulated Emission of Radiation is the phenomenon with the acronym LASER. In a pulsed laser. The blue shift was measured to be Δω = (5.
. made from the same material as the emitter. Our equations show that the decay rate of a state by emission of a photon is proportional to the number (plus one) of photons in the ﬁeld (with the same wavenumber as the photon to be emitted). Now there is a population inversion in the Neon. That is. If this population inversion is achieved. the population of the excited state will become depleted and the light pulse will end until the inversion can be achieved again.
28. We need to circumvent equilibrium to make the LASER work. An excited Helium atom can deexcite in a collision with a Neon atom. To cause many more photons to be emitted than are reabsorbed a LASER is designed to produce a poplation inversion. we ﬁnd a way to put many more atoms in the excited state than would be the case in equilibrium. In normal equilibrium.12. The Helium states can’t make an E1 transition so they are likely to excite a Neon atom instead.414 The M¨ssbauer eﬀect has be used to measure the gravitational red shift on earth. t)
=
2π¯ c2 h ωV
ˆ
√ i(k·r−ωt) √ Ne + N + 1e−i(k·r−ωt)
Here “plus one” is not really important since the number of photons is very large.13 ± 0.92 × 10−15 was expected based upon the general principle of equivalence. at a velocity (should be equal to the free fall velocity). Assume this material has an excited state that can decay by the emission of a photon to the ground state. For example. the LASER uses stimulated emission to genrate an intense pulse of light. It turns out that the ﬁrst and second excited states of Helium have almost the same excitation energy as the 4s and 5s excitations of Neon. If a high voltage is applied and an electric current ﬂows through the gasses.51) × 10−15 ω when 4. As the name would indicate. then the LASER can run continously. both atoms can be excited. Lets assume the material we wish to use is in a cavity. there will be many more atoms in the ground state and transitions from one state to the other will be in equilibrium and black body radiation will exist in the cavity. a HeliumNeon LASER has a mixture of the two gasses.
but some of the radiation leaks out to make the beam.
high voltage
. A laser with a beam coming out if it would be made in a cavity with a half silvered mirror so that the radiation can build up inside the cavity. The metastable state will have a much larger population than in equilibrium. A normal light sorce can excite a higher excited state which decays to a metastable excited state.415
2 1S 0
collision
(2p) (5s)
5
visible laser
2 3S 1
collision
(2p) (4s)
5
IR laser
(2p) (3p)
5
(2p) (3s)
5
1 1S 0
(2p)
6
He
Ne
Another way to get the population inversion is just the use of a metastable state as in a ruby laser.
14.1
Examples
The 2P to 1S Decay Rate in Hydrogen
28. d3 n = V d3 p (2π¯ )3 h
Using Fermi’s Golden Rule as a basis. we have two particles in the ﬁnal state and the delta function of momentum conservation will do one of the 3D integrals getting us back to the same result. for example. of an atom decaying by the emission of one photon. Our phase space calculation for photons was correct even for particles with masses. E B = = − 1 ∂A ω = 2 A0 sin(k · r − ωt) c ∂t c ∇ × A = 2k × A0 sin(k · r − ωt)
Note that. The energy density in the ﬁeld is U= 1 1 4 E2 + B2 = 8π 8π ω2 2ω 2 2 2 + k 2 A2 sin2 (k · r − ωt) = A sin (k · r − ωt) 0 c2 2πc2 0
Averaging the sine square gives one half.13
28. we must consider the number of states available for each one.416
28. so. t) ≡ 2A0 cos(k · r − ωt). We have not bothered to deal with the free particle wave function of the 1 recoiling atom.14
28. we include the general phase space formula into our formula for transition rates. the vector potential is transverse to the wave vector.
N
Γi→f =
k=1
V d3 pk (2π¯ )3 h
k
Mf i 2 δ
Ei − Ef −
k
Ek
δ3
pi − pf −
pk
In our case.
. for an EM wave. which will give the factor of V to cancel the V in the phase space for the atom.2
General Phase Space Formula
If there are N particles in the ﬁnal state.13.1
Derivations and Computations
Energy in Field for a Given Vector Potential
We have the vector potential A(r.14. First ﬁnd the ﬁelds. the energy in a volume V is Energy = ω 2 A2 V 0 2πc2
28.
5. Magnetic dipole transitions are due to an axial vector operator and hence are proportional to the Y1m but do not change parity (unlike a vector operator). Find the selection rules for E2 transitions. and are parity even. Draw the energy level diagram for hydrogen up to n = 3. Quantitatively compare the natural line width to the widths from Doppler broadening and collision broadening expected for radiation from the sun’s surface. Photons from the 3p → 1s transition are observed coming from the sun. What are the M1 selection rules? 3.51 MeV )3 × 1010 cm/sec −13 (10 F/cm) ≈ 2 × 1010 sec−1 = (1375 )(197 MeV F )
This gives a life time of about 50 psec. Assume that we prepare Hydrogen atoms in the ψn m = ψ211 state. What is the probability that a photon with its wave vector pointing along the axis will be Left Circularly Polarized? 7. Calculate the decay rate for the 3d → 2p transition in hydrogen. 6.3 Estimate of Atomic Decay Rate
We have the formula Γtot = Lets make some approximations.
.
28.417 28. Y2m . ˆ· p k·r e−i(k·r) Γtot
e2 (Ei − En ) 2π¯ 2 m2 c3 h
dΩγ  φn e−i(k·r) ˆ · pe φi 2
≈ p = mv ≈ mαc = αmc 1 2 α mc2 h α h ¯ω α2 mc2 ¯ a0 ≈ 2 a0 = = ≈ ka0 = h ¯c h ¯c 2¯ c αmc h 2 iα iα ≈1 ≈ e 2 ≈1+ 2 e2 (Ei − En ) = (4π)αmc2 2π¯ 2 m2 c3 h α(Ei − En ) = (4π)αmc2 2π¯ m2 c2 h α( 1 α2 mc2 ) 2 = (4π)αmc2 2π¯ m2 c2 h α5 mc2 = h ¯ α5 mc2 c = h ¯c (0. Calculate the decay rate for the 3p → 1s transition. 2.15
Homework Problems
1. We set up an experiment with the atoms at the origin and detectors sensitive to the polariztion along each of the 3 coordinate axes. 4.14. The interaction term for Electric Quadrupole transitions correspond to a linear combination of spherical harmonics. Show the allowed E1 transitions. Use another color to show the allowed E2 and M1 transitions.
)
. (You may use the solutions of the 3D harmonic oscillator problem from the notes. An electron is bound in a spherically symmetric 3D harmonic oscillator potential V (r) = 1 mω 2 r2 .418 8. 2 Assume that the ¯ ω << mc2 so that the Electric Dipole approximation is very good. Calculate h the decay rate of an oscillator in the 1d state to the 0p state.
s. These are rules for the allowed changes in l. Assume that a heavy nucleus attracts K0 mesons with a weak Yakawa potential V (r) = V0 e−αr . Draw an energy level diagram (up to n = 3) for hydrogen atoms in a weak B ﬁeld.16
Sample Test Problems
1. 4. A hydrogen atom is in the n = 5. 5. To which states is it allowed to decay via electric 2 dipole transitions? What will be the polarization for a photon emitted along the zaxis if ml decreases by one unit in the decay? 2. and with ( = − 1). m. m. 0
2 +1
The formula sheet gives R21 but we need to determine the normalization constant for R32 . These are rules for the change in l. Show the allowed E1 transitions from n = 3 to n = 1 on that diagram. State the selection rules for radiative transitions between hydrogen atom states in the electric dipole approximation. Derive the selection rules for radiative transitions between hydrogen atom states in the electric dipole approximation. Calculate the total decay rate for the 3d → 2p transition in hydrogen. They can be easily derived from the matrix element given on the front of the test. Be sure to write your answer in terms of the scattering angles. 2 D 5 state. for scattering high energy K0 mesons (mass mK ) from that nucleus.419
28. dΩ . from a spherical shell delta function
dσ dΩ . and parity. 3. r dσ Calculate the diﬀerential cross section. What is the lifetime in nanoseconds? (10 points) For an unpolarized initial state and summing over ﬁnal atomic states (mf ). and s. 6.
V (r) = λ δ(r − r0 ) Assume that the potential is weak so that perturbation theory can be used.
for high energy scattering of particles of momentum p. the total decay rate is Γtot
3 4αωin = 3c2 ∞ 2 ∗ Rn Rn r3 dr . Calculate the diﬀerential cross section. Give your answer in terms of the scattering angle θ.
∞
R32 r2 r4 e−2r/3a0 dr
= Cr2 e−r/3a0 = 1
C
2 0
C 2 6!
2 3a0
−7
= 1 C2 = 1 6!
2 0
2 3a0
∞ 3
7
∞ ∗ Rn 0
2
Rn r dr
3
= C
1 r √ 3
7
1 2a0 1 2a0
3 2
2
r a0 1 a2 0
∞
e
−r 2a0
r e
2 −r/3a0
dr
=
1 6!
2 3a0
1 3
3
2
r6 e
0
−5r 6a0
dr
.
5 × 109 s−1 = 0.154 nsec = Γ = 16 24 25
7
.0040 1375(1973eV A)(10−10 cm/A) 1 = 0.420
7 2
=
1 6!
2 3a0 2 3a0 4 5 24 25
7
7
1 3 1 3
1 2a0 1 2a0
3
1 6! a2 0 1 a2 0
6a0 5
7
3
= 6! = 6! = 6! Γtot =
6a0 5 6a0 5
7
7 2
1 3
7
1 2a0
3
1 a2 0
1 2 a = 30 24 0 24 25
7
24 25
7
a2 0 24 25
7 5 α ( 72 α2 mc2 )3
3 4αωin 2 30 2 5 3c
a2 = 16 0
3
h ¯ 3 c2
h ¯ αmc
2
τ
5 α5mc2 c α5 mc2 = 0.0040 72 h ¯ h ¯c 10 (511000eV )(3 × 10 cm/s) = 6.
This is a well deﬁned quantity in quantum mechanics. we have a beam of particles and we know the number of particles per second. For example.421
29
Scattering
This material is covered in Gasiorowicz Chapter 23. Let us take the macroscopic example of BBs scattering from billiard balls as an example to study.
.25 microns. and R is the radius of the billiard ball. Ratescat = N πR2 = (Incident AT F lux)(cross section)
The incident ﬂux is the number of particles per unit area per unit time in the beam. j. The cross section σ is the projected area of the billiard ball in this case. We can fairly easily calculate how billiard balls would scatter if the collisions were elastic but with some energy loss and the possibility of transfer of energy to spin. the calculation becomes more diﬃcult. the cross section for scattering is σ = π(R + r)2 . In normal scattering experiments. We measure the number of scatters per second so we just divide the above equation by the time period T to get rates. If we hit. Since the minimum wavelength of visible light is about 0. nuclei. and the fundamental particles and interactions in nature must be studied by scattering particles of higher energy than the photons of visible light. Scattering is also something that we are familiar with from our every day experience. If we miss the BB does not scatter. We will motivate some of the terminology used in scattering macroscopically. We can learn the shapes of objects as well as some color properties simply by observing scattered light. Assume we ﬁre a BB at a billiard ball. For example. There is a limit to what we can learn with visible light. Assume our aim is bad and that the BB has a uniform probability distribution over the area around the billiard ball. We can then say something about the probability for a scattering to occur if we know the area of the projection of the billiard ball and number of BBs per unit area that we shot. Indeed it is the scattering of light from objects and the subsequent detection of the scattered light with our eyes that gives us the best information about the macroscopic world. the BB bounces oﬀ the ball and goes oﬀ in a direction diﬀerent from the original direction. A is the area over which they are spread. The physics of atoms. In Quantum Mechanics we know that we cannot discern details of microscopic systems (like atoms) that are smaller than the wavelength of the particle we are scattering. billiard balls scatter from each other in a predictable way. we cannot see atoms or anything smaller even with the use of optical microscopes. Assume the BB is much smaller so that its radius can be neglected for now. if we do not neglect the radius r of the BB. subatomic particles. Scattering of one object from another is perhaps our best way of observing and learning about the microscopic world. Nscat = N πR2 A
Where N is the number of BBs we shot. The area of the projection of the billiard ball into two dimensions is just πR2 if R is the radius of the billiard ball. It may be more complicated in other cases.
that is a beam of particles of deﬁnite momentum or wave number. φ) = f (θ. The scattered particle is also a plane wave going in the direction deﬁned by dΩ. This will also happen in the case of the BB and the billiard ball. dσ dΩ f (θ. If we calculate this phase shift δ . The atomic model of the time did not allow this since the positive charge was spread over a large volume. It is good for scattering potentials of limited range and for low energy scattering. we can then determine the diﬀerential scattering cross section.6) . The polar angle of scattering will depend on the “impact parameter” of the incoming BB. We may then deal with just the ﬁrst few terms (or even just the = 0 term) in the expansion. We have already studied one approximation method for scattering called a partial wave analysis (See section 14. φ) = 1 k
2
(2 + 1)eiδ
(k)
sin(δ (k))P (cos θ) =
f (θ. If the incoming beam is a plane wave.
∞ ∞
eikz = eikr cos θ =
=0
4π(2 + 1)i j (kr)Y
0
→−
=0
4π(2 + 1)i
1 e−i(kr− 2ikr
π/2)
− ei(kr−
π/2)
Y
0
A potential causing elastic scattering will modify the phases of the outgoing spherical waves.
∞ r→∞
lim ψ = −
=0
4π(2 + 1)i
1 e−i(kr− 2ikr
π/2)
− e2iδ
(k) i(kr− π/2)
e
Y
0
We can compute the diﬀerential cross section for elastic scattering. For example. The high angular momentum components of the wave will not scatter (much) because they are at large distance from the scattering potential where that potential is very small. φ)
. It divides the incoming plane wave in to partial waves with deﬁnite angular momentum. we can describe it simply in terms of the number or particles per unit area per second. What is left is the interaction between the target particle and the beam particle which causes the transition from the initial plane wave state to the ﬁnal plane wave state. Rutherford discovered that atomic nucleus by seeing that high energy alpha particles sometimes backscatter from a foil containing atoms. A plane wave can be decomposed into a sum of spherical waves with deﬁnite angular momenta which goes to a simple sum of incoming and outgoing spherical waves at large r. We showed that the incoming partial wave and the outgoing wave can diﬀer only by a phase shift for elastic scattering. the incident ﬂux. dσ 1 = 2 dΩ k
2
(2 + 1)e
iδ (k)
sin(δ (k))P (cos θ)
It is useful to write this in terms of the amplitudes of the scattered waves. Let’s review some of the equations.422 Clearly there is more information available from scattering than whether a particle scatters or not. dσ dΩ = σ dΩ The idea of cross sections and incident ﬂuxes translates well to the quantum mechanics we are using. We measure the probability to scatter into diﬀerent directions. The integral over solid angle will give us back the total cross section. The part of the cross section σ that scatters into that solid angle can dσ be called the diﬀerential cross section dΩ . We can measure the scattering into some small solid angle dΩ.
∞ r→∞
lim ψ = −
=0
4π(2 + 1)i
1 e−i(kr− 2ikr
π/2)
− η (k)e2iδ
(k) i(kr− π/2)
e
Y
0
.7) assuming only the = 0 phase shift was signiﬁcant. tan δ0 = − The diﬀerential cross section is k cos(ka) sin(k a) − k cos(k a) sin(ka) C = B k sin(ka) sin(k a) + k cos(k a) cos(ka) dσ sin2 (δ0 ) → dΩ k2 k cot(k a) = k cot(ka). the electrons appeared to be scattering from essentially free quarks inside the proton. even when elastic and inelastic processes are possible. inelastic scattering removes ﬂux from the outgoing spherical waves. The total cross section corresponds to removal of ﬂux from the plane wave. It can be understood in terms of removal of ﬂux from the incoming plane wave. This seemingly strange relation is known as the Optical Theorem. φ) dΩ 4π k2 1 k
2
which will have zeros if
dΩP (cos θ)P (cos θ) =
4π 2 +1 δ
. φ)] = σtot = 1 k 1 k (2 + 1)eiδ
(k)
sin(δ (k))
(2 + 1) sin2 (δ (k))
4π Im [f (θ = 0. It was with high energy inelastic scattering of electrons from protons that the quark structure of the proton was “seen”. In fact. for which P (1) = 1. In a phase shift analysis. The proton was broken up into sometimes many particles in the process but the data could be simply analyzed using the scatter electron. we determined the phase shift. Remember we have an incoming plane wave plus scattered spherical waves.423 As an example. By matching the boundary conditions at the boundary of the spherical well. Since the plane wave is at θ = 0 it is only the scattered amplitude at θ = 0 that can interfere. It is therefore reasonable that a relation like the Optical Theorem is correct. We can compute the total scattering cross section using the relation σtot = = = dΩ f (θ. We have not treated inelastic scattering. Inelastic scattering can be a complex and interesting process.
(2 + 1)eiδ
(k)
sin(δ (k))P (cos θ)
1 k
(2 + 1)e−iδ
(k)
sin(δ (k))P (cos θ)
(2 + 1) sin(δ (k))2
It is interesting that we can relate the total cross section to the scattering amplitude at θ = 0. f (θ = 0. φ)] k
The total cross section is related to the imaginary part of the forward elastic scattering amplitude. this has been used to compute the cross section for scattering from a spherical potential well (See section 14. φ) = Im [f (θ = 0. The only way to do this is destructive interference with the scattered waves.
V We can use Fermi’s golden rule to calculate the transition rate to ﬁrst order in perturbation theory. Ri→f = 2π h ¯ V d3 kf 2  ψf V (r)ψi  δ(Ef − Ei ) (2π)3
The delta function expresses energy conservation for elastic scattering which we are assuming at this point. the removal of the outgoing spherical partial waves modiﬁes the plane wave to include scattered waves. The elastic scattering matrix element is ψf V (r)ψi = 1 V d3 re−ikf ·x V (r)eiki ·x = 1 V d3 re−iΔ·x V (r) = 1 ˜ V (Δ) V
where Δ = kf − ki . V The scattered plane wave is 1 ψf (r) = √ eikf ·x . To do this we set the volume to be
. Our wave functions are normalize to one particle per unit volume and we should modify that so that there is a ﬂux of one particle per square centimeter per second to get a cross section. We notice that this is just proportional to the Fourier Transform of the potential. a partial wave analysis is not helpful and it is far better to use perturbation theory. we have a problem with one particle scattering in a potential. Somewhat surprisingly the total elastic scattering cross section is σelas = πa2 . The disk absorbs part of the beam and there is also diﬀraction around the sharp edges.424 Here 0 < η < 1. If we work in the usual center of mass system. For high energies relative to the inverse range of the potential. the energy of the atomic state changes and that change should be included in the delta function and the change in the atomic state should be included in the matrix element. with 0 represent complete absorption of the partial wave and 1 representing purely elastic scattering. If the potential is weak. one ﬁnds that there is an inelastic scattering cross section of σinel = πa2 . only one or two terms in the perturbation series need be calculated. The incoming plane wave can be written as 1 ψi (r) = √ eiki ·x . That is. The disk has a deﬁnite radius a and absorbs partial waves for < ka. If one works out this problem. If inelastic scattering is to be calculated. Assuming for now nonrelativistic ﬁnal state particles we calculate Ri→f = = = 2π h ¯
2 2 V dΩf kf dkf 1 ˜ V (Δ) δ (2π)3 V2
h 2 ¯ 2 kf − Ei 2μ
2 2π 1 μ 2 ˜ dΩf kf V (Δ) 2 3V h ¯ (2π) h ¯ kf 2 1 ˜ dΩf μkf V (Δ) 4π 2 ¯ 3 V h
We now need to convert this transition rate to a cross section. An interesting example of the eﬀect of absorption (or inelastic production of another state) is the black disk. The Born approximation is valid for high energy and weak potentials.
It is not good for scattering due to the strong interaction since cross sections are large and do not typically decrease at high energy.
∞ 1
˜ V (Δ)
= Z1 Z2 e 2π
0 ∞
2
r dr
−1
2
d(cos θ)e−iΔr cos θ e−iΔrx −iΔr
x=1 x=−1
e−r/a r
= Z1 Z2 e2 2π
0 2 2π
r2 dr
∞
e−r/a r
= Z1 Z2 e
iΔ
0 2
dr e−iΔr − eiΔr e−r/a
∞
1 1
2π = Z1 Z2 e −iΔ
dr e−( a +iΔ)r − e−( a −iΔ)r
0
.
29. The relative velocity is just the momentum divided by the reduced 1 ˜ dΩf μkf V (Δ) 2¯ 3v 4π h rel 2 1 ˜ dΩf μ2 V (Δ) 4 4π 2 ¯ h 2 μ2 ˜ V (Δ) 2¯ 4 4π h
2
σ
= =
dσ dΩ
=
This is a very useful formula for scattering from a weak potential or for scattering at high energy for problems in which the cross section gets small because the Fourier Transform of the potential diminishes for large values of k. cm2 )(vrel )(1 second). ˜ V (Δ) = Z1 Z2 e2 d3 re−iΔ·r e−r/a r Z1 Z2 e2 −r/a e r
Since the potential has spherical symmetry. Note that the matrix elements and hence the scattering amplitudes calculated in the Born approximation are real and therefore do not satisfy the Optical Theorem. the total Coulomb scattering cross section is inﬁnite because the range of the force in inﬁnite. that is. we can choose Δ to be in the z direction and proceed with the integral.425 V = (1 mass.1
Scattering from a Screened Coulomb Potential
A standard Born approximation example is Rutherford Scattering. The exponential represents the screening of the nuclear charge by atomic electrons. This is a shortcoming of the approximation. Without screening. Coulomb scattering of a 2 particle of charge Z1 e in a screened Coulomb potential φ(r) = Zr e e−r/a . The potential energy then is V (r) = We need to calculate its Fourier Transform.
29. we have Δ2 = kf + ki − 2kf ki cos θ. We will assume that h ¯ kr0 < ¯ so that only the = 0 partial wave is signiﬁcantly aﬀected by the sphere. For elastic scattering. The diﬀerential cross section is
dσ dΩ
= =
2 μ2 ˜ 4 V (Δ) 4π 2 ¯ h 2 μ 4πZ1 Z2 e2 1 4π 2 ¯ 4 a2 + 2k 2 (1 − cos θ) h
2
=
μZ1 Z2 e2
h2 ¯ 2a2
2
+ p2 (1 − cos θ) Z1 Z2 e2
2 θ 2 1 2
=
h2 ¯ 2μa2
+ 4E sin2
In the last step we have used the nonrelativistic formula for energy and 1 − cos θ =
sin2 θ . we can take the limit in which a → ∞. hard sphere of radius r0 .2
Scattering from a Hard Sphere
Assume a low energy beam is incident upon a small. So we set e−i(kr0 −
π/2)
− e2iδ
(k) i(kr0 − π/2)
e
= e−ikr0 − e2iδ0 (k) eikr0 = 0 e2iδ0 (k) = e−2ikr0
. If we scatter from a bare charge where there is no screening. Z1 Z2 e2 4E sin2 θ 2
2
The total cross section diverges in due to the region around zero scattering angle. the potential is zero and the wavefunction solution will have reached its form for large r. As with the particle h in a box.426 e−( a +iΔ)r 2π e−( a −iΔ)r − 1 = Z1 Z2 e + 1 −iΔ a + iΔ a − iΔ
2
1 1
∞
0
2π = Z1 Z2 e2 −iΔ = Z1 Z2 e2 = Z1 Z2 e2 = 2π −iΔ 2π −iΔ
1 a 1 a
1 − + iΔ −
1 a 1 iΔ − a − 1 2 a2 + Δ
1 − iΔ iΔ
1 a2
−2iΔ + Δ2
4πZ1 Z2 e2 1 2 a2 + Δ
2 2 Since Δ = kf − ki . Δ2 = 2k 2 (1 − cos θ). the boundary condition on a hard surface is that the wavefunction is zero. 2
The screened Coulomb potential gives a ﬁnite total cross section. It corresponds well with the experiment Rutherford did in which α particles were scattered from atoms in a foil. Outside the sphere.
Give your answer in terms of the scattering angle θ.427 δ0 (k) = −kr0 2 1 iδ (k) dσ = 2 e sin(δ (k))P0 (cos θ) dΩ k 1 dσ 2 = 2 e−ikr0 sin(kr0 ) dΩ k sin2 (kr0 ) dσ = dΩ k2 For very low energy. 2.
29. dΩ . for scattering high energy K0 mesons (mass mK ) from that nucleus. Photons from the 3p → 1s transition are observed coming from the sun. r dσ Calculate the diﬀerential cross section.
1. Be sure to write your answer in terms of the scattering angles. Quantitatively compare the natural line width to the widths from Doppler broadening and collision broadening expected for radiation from the sun’s surface.
29.
. kr0 << 1 and
dσ (kr0 )2 2 ≈ = r0 dΩ k2
2 The total cross section is then σ = 4πr0 which is 4 times the area of the hard sphere. Assume that a heavy nucleus attracts K0 mesons with a weak Yakawa potential V (r) = V0 e−αr .3
Homework Problems
1.4
Sample Test Problems
dσ dΩ . Calculate the diﬀerential cross section.
V (r) = λδ(r − r0 ) Assume that the potential is weak so that perturbation theory can be used. from a spherical shell delta function
for high energy scattering of particles of momentum p.
Nevertheless. We start with the Lagrangian of a discrete system like a single particle. learn to write our equations in a covariant way in four dimensions. In this chapter. the physics of the electromagnetic. by the 1960s. The emphasis will be on learning how all these things work and on getting practice with calculations. In 1940. By now. we will start with simple ﬁeld theories to get some practice. and strong interactions are well described by Quantum Field (Gauge) Theories that together from the Standard Model. Quantum Field Theory (QFT) was quite successful in describing all detailed experiments in electromagnetic interactions and many aspects of the weak interactions. based on the hypothesis of Planck from the late 19th century. By about 1928. It assumes that a particle has a probability that integrates to one over all space and that the particles are not created or destroyed. q) = T − V ˙ Lagrange’s equations are d dt ∂L ∂ qi ˙ − ∂L =0 ∂qi
. we review the equations of a string as an example of a ﬁeld theory in one dimension. This all changed dramatically around 1970 when very successful Gauge Theories of the strong and weak interactions were introduced. The theory neither deals with the quantized electromagnetic ﬁeld nor with the relativistic energy equation. L(q. with the ﬁelds for bosons and fermions treated in a symmetric way. when our textbook was written. Pauli proved the spinstatistics theorem which showed why spin onehalf particles should behave like fermions and spin zero or spin one particles should have the properties of bosons. we must treat the propagation of photons relativistically. Dirac’s relativistic theory of electrons introduced many new ideas such as antiparticles and four component spinors.428
30
Classical Scalar Fields
The nonrelativistic quantum mechanics that we have studied so far developed largely between 1923 and 1925. yet behaving quite diﬀerently. weak. had been developed by Dirac.
30. we will review classical ﬁeld theory. Hence we will work toward understanding relativistic QFT. relativistic theories. not on mathematical rigor.1
Simple Mechanical Systems and Fields
This section is a review of mechanical systems largely from the point of view of Lagrangian dynamics. While we already have a good deal of knowledge about classical electromagnetism. It was not long after the nonrelativistic theory was completed that Dirac introduced a relativistic theory for electrons. in which the electromagnetic ﬁeld was quantized and the creation and absorption of particles was possible. and recall aspects of Lagrangian and Hamiltonian formalisms for use in ﬁeld theory. most particle theorists were doubtful that QFT was suitable for describing the strong interactions and some aspects of the weak interactions. In particular. As we quantize the EM ﬁeld. Quantum Mechanics became a quantum theory of ﬁelds.
qi )dt = 0 ˙
Similarly. this would be. L= For example. pi = ∂L ∂ qi ˙
For a continuous system. ∂ ∂x ∂L ∂(∂η/∂x) + ∂ ∂t ∂L ∂(∂η/∂t) − ∂L =0 ∂η
Recall that the Lagrangian is a function of η and its space and time derivatives. The string has a displacement at each point along it which varies as a function of time. L = ∂ ∂x ∂L ∂(∂η/∂x) + ∂ ∂t ∂L ∂(∂η/∂t) − ∂L ∂η = = 1 μη 2 − Y ˙ 2 0 −Y ∂η ∂x ∂η ∂x
2
∂L ∂(∂η/∂x)
. For the string. If we apply the EulerLagrange equation. L= 1 μη 2 − Y ˙ 2 ∂η ∂x
2
Ldx
where Y is Young’s modulus for the material of the string and μ is the mass density. η(x. we get a diﬀerential equation that the string’s displacement will satisfy. t) is a simple scalar ﬁeld. for a string. like a string.429 where the qi are the coordinates of the particle. the Lagrangian is an integral of a Lagrangian density function.
t2
δ
t1
L(qi . The Hamiltonian density can be computed from the Lagrangian density and is a function of the coordinate η and its conjugate momentum. pi ) =
i
pi qi − L ˙
where pi are the momenta conjugate to the coordinates qi . we can deﬁne the Hamiltonian H(qi . The EulerLagrange Equation for a continuous system is also derivable from the principle of least action states above. This equation is derivable from the principle of least action. H=η ˙ ∂L −L ∂η ˙
In this example of a string.
x1 ... x3 . So while we may have said “farewell to ict” some time in the past. z) and use the former to do real computations. (The convention does not really matter and one should not get hung up on it. not an indication of the need for complex numbers in our coordinate systems. ν. x2 . y. The Greek indices like μ. will run from 1 to 3 and represent the space coordinates. We can assume the i in the fourth component is a calculational convenience.. there is no need for the complication of a metric tensor to raise and lower indices unless general relativity comes into play and the geometry of spacetime is not ﬂat. Since we are aiming for a description of relativistic quantum mechanics. but. λ.430 ∂L ∂(∂η/∂t) −Y
=
μη ˙ 0 Y ∂2η μ ∂x2
∂2η + μ¨ + 0 = η ∂x2 η = ¨
This is the wave equation for the string. As Sakurai points out. Sakurai would give the spacetime coordinate vector either as (x1 . z. x3 ) = (t.. will run from 1 to 4. x. t) = φ (r . x4 ) = (x.2
Classical Scalar Field in Four Dimensions
Assume we have a ﬁeld deﬁned everywhere in space and time.
30. k. ict) or as (x0 . there is only one equation. as we move away from simple mechanical systems. t ) The EulerLagrange equation derived from the principle of least action is ∂ ∂xk ∂L ∂(∂φ/∂xk ) + ∂ ∂t ∂L ∂(∂φ/∂t) − ∂L = 0. φ(r. x2 . we will use it here because the notation is less complicated. xμ xμ = x2 + y 2 + z 2 − c2 t2 Note we can have all lower indices. ﬁelds of E&M). For simplicity we will start with a scalar ﬁeld (instead of the vector. I think this also simpliﬁes the equations. t) The property that makes this a true scalar ﬁeld is that it is invariant under rotations and Lorentz boosts. Instead we will put an i on the fourth component of a vector which give that component a − sign in a dot product. σ. There are easier ways to get to this wave equation.. j.) As usual the Latin indices like i. ∂φ
k
Note that since there is only one ﬁeld. We will not use the so called covariant and contravariant indices. y.. it will beneﬁt us to write our equations in a covariant way. The
. φ(r. We will follow the notation of Sakurai. a formal way of proceeding will be very helpful.
We can compute this from the transformations and the chain rule. Since we are in Minkowski space where we need a minus sign on the time component of dot products. xμ = aμν xν (Note that we will always sum over repeated indices. we need to add an i in this rotation too. xμ = aνμ xν Vectors transform as we change our reference system by rotating or boosting. Thus we may compute the coordinate using the inverse transformation. 0 0 1 0 0 0 0 1 A boost along the x direction is like a rotation in the xt through an angle of θ where tanh θ = β.431 i here should never really be used to multiply an i in the complex wave function. Higher rank tensors also transform with one Lorentz transformation matrix per index on the tensor. We need to know what the transformation properties of this are. For example. a Lorentz boost is a rotation in which tan iθ = β. The Lorentz transformation matrix to a coordinate system boosted along the x direction is. L (x ) = L(x) The Lagrangians we have seen so far have derivatives with respect to the coordinates. The 4vector way ∂ of writing this will be ∂xμ . Latin or Greek. The spacetime coordinate xμ is a Lorentz vector transforming under rotations and boosts as follows. ⎛ ⎞ γ 0 0 iβγ 1 0 0 ⎟ ⎜ 0 aμν = ⎝ ⎠ 0 0 1 0 −iβγ 0 0 γ The i shows up on spacetime elements to deal with the i we have put on the time components of 4vectors.) The Lorentz transformation is done with a 4 by 4 matrix with the property that the inverse is the transpose of the matrix. everything will work out so that doesn’t happen unless we make an algebra mistake. ⎛ ⎞ ⎛ ⎞ ⎛ ⎞ cos iθ 0 0 sin iθ cosh θ 0 0 i sinh θ γ 0 0 iβγ 1 0 0 ⎟ ⎜ 0 1 0 0 ⎟ ⎜ 0 1 0 0 ⎟ ⎜ 0 aμν = ⎝ ⎠=⎝ ⎠=⎝ ⎠ 0 0 1 0 0 0 1 0 0 0 1 0 − sin iθ 0 0 cos iθ −i sinh θ 0 0 cosh θ −iβγ 0 0 γ Eﬀectively. but. a−1 = aνμ μν The aij and a44 are real while the a4j and aj4 are imaginary in our convention. our Lagrangian density should be invariant. xν ∂ ∂xμ = = aμν xμ ∂xν ∂ ∂ = aμν ∂xμ ∂xν ∂xν
. We will make essentially no use of Lorentz transformations because we will write our theories in terms of Lorentz scalars whenever possible. It is interesting to note the similarity between Lorentz boosts and rotations. A rotation in the xy plane through an angle θ is implemented with the transformation ⎛ ⎞ cos θ sin θ 0 0 ⎜ − sin θ cos θ 0 0 ⎟ aμν = ⎝ ⎠.
The Lagrangian depends on the φ and its derivatives. Compare it to our original transformation formula for xμ . The overall constant is not important except to match the T − V deﬁnition.
∂ ∂xμ
∂L ∂(∂φ/∂xμ )
−
∂L =0 ∂φ
Now we want to ﬁnd a reasonable Lagrangian for a scalar ﬁeld. With this Lagrangian. With this. ∂ ∂xk ∂L ∂(∂φ/∂xk ) + + ∂ ∂t ∂L ∂(∂φ/∂t) − − − ∂L =0 ∂φ ∂L =0 ∂φ ∂L =0 ∂φ
k
k
∂ ∂xk
∂L ∂(∂φ/∂xk )
∂ ∂(ict) ∂ ∂xμ
∂L ∂(∂φ/∂(ict)) ∂L ∂(∂φ/∂xμ )
This is the EulerLagrange equation for a single scalar ﬁeld. It was also an early candidate for the relativistic equivalent of the Schr¨dinger equation o for electrons because it basically has the relativistic analog of the energy relation inherent in
. We also want to come out with a linear wave equation so that high powers of the ﬁeld should not appear. xμ = aμν xν We may safely assume that all our derivatives with one index transform as a vector. ∂ ∂xμ ∂φ + μ2 φ = 0 ∂xμ ∂ ∂ φ − μ2 φ = 0 ∂xμ ∂xμ − 2φ − μ2 φ = 0
This is the known as the KleinGordon equation. since that would violate translation and/or rotation invariance. the EulerLagrange equation is. Remember that φ is a function of the coordinates. It should not depend explicitly on the coordinates xμ . Each term in this equation is a Lorentz scalar. if L is a scalar.432 This means that it transforms like a vector. The only Lagrangian we can choose (up to unimportant constants) is 1 ∂φ ∂φ L=− + μ2 φ2 2 ∂xν ∂xν The one constant μ sets the ratio of the two terms. Remember that the ﬁeld φ is a Lorentz scalar. It is a good relativistic equation for a massive scalar ﬁeld. lets work on the EulerLagrange equation to get it into covariant shape.
There are no sources of the ﬁeld (the equivalent of charges and currents in electromagnetism. unlike the nonrelativistic Schr¨dinger equation.) So far we have the Lagrangian and wave equation for a “free” scalar ﬁeld. This is a ﬁeld that falls oﬀ much faster than 1 . It does not change with time so we expect a static ﬁeld. −p2 + E 2 − m2 = 0 Its worth noting that this equation. ∇2 φ − μ2 φ = Gδ 3 (x) We will solve this for the ﬁeld from a point source below and get the result φ(x) = −Ge−μr .) Lets assume the source density is ρ(xμ ). t) = ρ(xμ ) = Gδ 3 (x) This is a source of strength G at the origin. ∂φ =0 ∂t The EulerLagrange equation becomes. Writing that relation in the order terms appear in the KleinGordon equation o above we get (letting c = 1 brieﬂy). ˜ φ(k) = φ(x) = 1 (2π) 2 1 (2π) 2
3 3
d3 x e−ik·x φ(x) ˜ d3 k eik·x φ(k)
We now take the transform of both sides of the equation. r Now we solve for the scalar ﬁeld from a point source by Fourier transforming the wave equation. L=− This adds a term to the wave equation. ∇2 φ = −ρ = −Qδ 3 (x). r A massive scalar ﬁeld falls oﬀ exponentially and the larger the mass. The source term must be a scalar function so. ρ(x.433 the Schr¨dinger equation. we add the term φρ to the Lagrangian. the faster the fall oﬀ. Deﬁne the Fourier transforms to be. (Remember the Schr¨dinger equation o has i times the ﬁrst time derivative as the energy operator. This is worked out another way in the section on hyperﬁne splitting) ∇2 1 = −4πδ 3 (x). ∇2 φ − μ2 φ = Gδ 3 (x)
. relates the second o spatial derivative of the ﬁeld to the second time derivative. (We also get a mathematical result which is useful in several applications. 2φ − μ2 φ = ρ Any source density can be built up from point sources so it is useful to understand the ﬁeld generated by a point source as we do for electromagnetism. 4πr 1 2 ∂φ ∂φ + μ2 φ2 ∂xν ∂xν + φρ
This solution should be familiar to us from the scalar potential for an electric point charge which satisﬁes the same equation with μ = 0.
k ikr dk around a contour in the upper half plane as shown below. If we can transform back to position space. we have integrated by parts twice assuming that the ﬁeld falls oﬀ fast enough at inﬁnity. That’s easy to do since the integrand goes to zero at inﬁnity on the real axis and the exponentials go to zero either at positive or negative inﬁnity for the imaginary part of k. a pole is of the form k where r is called the residue at the pole. This is a fairly standard type of problem in quantum mechanics. Examine the integral (k+iμ)(k−iμ) e
.434 1 (2π) 1
3 2
d3 x e−ik·x (∇2 φ − μ2 φ) d3 x e−ik·x (∇2 φ − μ2 φ) d3 x e−ik·x (−k 2 − μ2 )φ
= = =
1 (2π) 2 G (2π) 2 G (2π) 2 G (2π) 2 −G (2π)
3 2 3 3 3 3
d3 x e−ik·x Gδ 3 (x)
(2π) 2 1 (2π) 2
3
3
˜ (−k 2 − μ2 )φ = ˜ φ =
(k 2
1 + μ2 )
To deal with the ∇2 . The integrand above has two poles. one at k = iμ and the other at k = −iμ.
r If the integrand is a function of the complex variable k. φ(x) = = 1 (2π)
3 2
d3 k eik·x d3 k
2
1 (k 2 + μ2 ) (2π)
3 2
−G
−G (2π)3 −2πG (2π)3 −G (2π)2 −G (2π)2 −G (2π)2 ir −G (2π)2 ir
eik·x (k 2 + μ2 )
1
=
k dk
−1
eikr cos θk d cos θk (k 2 + μ2 )
1
=
k2 (k 2 + μ2 )
2
eikr cos θk d cos θk dk
−1 1
= = =
1 ikr cos θk k e dk 2 + μ2 ) ikr (k −1 k eikr − e−ikr dk 2 + μ2 ) (k
∞
0
k eikr − e−ikr dk (k + iμ)(k − iμ)
This is now of a form for which we can use Cauchy’s theorem for contour integrals. Contour Integration is a powerful technique often used in quantum mechanics. We now have the Fourier transform of the ﬁeld of a point source. The theorem says that an integral around a closed contour in the complex plane is equal to 2πi times the sum of the residues at the poles enclosed in the contour. The integral we are interested in is just along the real axis so we want the integral along the rest of the contour to give zero. we will have the ﬁeld.
k eikr dk (k + iμ)(k − iμ)
∞
= 2πi
keikr k + iμ iμe iμ + iμ
−μr
k=iμ
−∞ 0
k eikr dk (k + iμ)(k − iμ) k eikr dk (k + iμ)(k − iμ) k
= 2πi
−∞ 0
k eikr dk + (k + iμ)(k − iμ)
∞
1 = 2πi e−μr 2 = −k = πie−μr
0 ∞
∞
−k e−ik r (−dk ) + (−k + iμ)(−k − iμ)
∞
0
k eikr dk (k + iμ)(k − iμ)
∞
−
0
k e−ik r dk + k 2 + μ2
k eikr dk k 2 + μ2 k k eikr dk k 2 + μ2
= πie−μr = k = πie−μr
0 ∞ ∞
−
0
k e−ikr dk + k 2 + μ2
0
. The integral along the real axis can be manipulated to do the whole problem for us. The residue at the pole is keikr k + iμ =
k=iμ
1 iμe−μr = e−μr .435
Imaginary
pole
ιμ −ιμ Real Axis
The pole inside the contour is at k = iμ. iμ + iμ 2
The integrand goes to zero exponentially on the semicircle at inﬁnity so only the real axis contributes to the integral along the contour.
Pions and nucleons have since been show to be composite particles with internal structure. He predicted a scalar particle with a mass close to that of the pion before the pion was discovered. Plug the integral into the Fourier transform we were computing. ρ(x. Lets assume we have two particles. Now we will attempt to do the same for classical electromagnetism. His prediction of the mass was based on the range of the nuclear force. Its not our goal right now so we will skip this. each with the same interaction with the ﬁeld. his prediction is approximately correct.436
∞ ∞
k eikr dk − 2 + μ2 k
∞
k2
0
k e−ikr dk + μ2
= πie−μr
0
k2
0
k + μ2
eikr − e−ikr dk
= πie−μr
This is exactly the integral we wanted to do.
. on the order of one Fermi. This was proposed by Yukawa as the nuclear force. φ(x) = φ(x) = φ(x) = −G (2π)2 ir
∞
k k 2 + μ2
eikr − e−ikr dk
0
−G πie−μr (2π)2 ir −Ge−μr 4πr
In this case. attractive potential. Pions were also found to come in three charges: π + .2)
= = = =
−φρ ˙ ∂Lint − Lint = −Lint = φρ φ ˙ ∂φ Hint d3 x2 φ1 ρ2 d3 x2 = −Ge−μr 3 −G2 e−μr12 Gδ (x2 )d3 x2 = 4πr 4πr12
We see that this is a shortrange. In some sense. Its interesting to note that the Higgs Boson is also represented by a complex scalar ﬁeld. Pion exchange can explain much of the nuclear force but does not explain all the details. We have developed a covariant classical theory for a scalar ﬁeld. t) = ρ(x) = Gδ 3 (x) Now compute the Hamiltonian. it is simple to compute the interaction Hamiltonian from the interaction Lagrangian and the potential between two particles. π − . This would lead us to develop a complex scalar ﬁeld as done in the text. We have included an interaction term to provide a source for the ﬁeld. and π 0 . The Lagrangian density is a Lorentz scalar function. Other composites with masses larger than the pion also play a role in the force between nucleons. Lint Hint Hint Hint
(1.
x. py .
x1
2. Explain the physical consequence of each of these c scalars being invariant.437
30. z) and the momentum fourvector pμ = ( E . pz ). Derive the EulerLaGrange equation for a scalar ﬁeld in one dimension η(x. px .
. y. η)dt = 0 ˙
where L=
x2
Ldx.3
Homework Problems
1. t) ∂ ∂x ∂L ∂(∂η/∂x) + ∂ ∂t ∂L ∂(∂η/∂t) − ∂L =0 ∂η
from the principle of least action given by
t2
δ
t1
L(η. Find three Lorentz scalar quantities made from the coordinate fourvector xμ = (ct.
We don’t need to change the centimeter. the formula for it does because we have redeﬁned the charge e. Physicists have more often used CGS units in which the unit of charge and deﬁnition of the ﬁeld units are set so that 0 = 1 and μ0 = 1 so they need not show up in the equations. E B → → E √ 4π B √ 4π √ 4π and
A → e e2 α= h ¯c
A √ 4π √ → e 4π e2 1 → ≈ 4π¯ c h 137
Its not a very big change but it would have been nice if Maxwell had started with this set of units. Of course the value of α cannot change. Therefore many important physical equations end up with extra (needless) constants in them like c. and we will want to change them slightly to make our theory of the Maxwell Field simple. As the name of the system of units suggests. Even with the three basic units deﬁned. the problem with CGS has been with π. In Rationalized HeavisideLorentz units we decrease the ﬁeld strength by a factor of increase the charges by the same factor. gram or second to ﬁx the problem. The mistake made in deﬁning CGS units was in removing the 4π that show up in Coulombs law. we could have chosen the unit of charge correctly to make −7 and the Ampere 0 and μ0 unnecessary but instead a very arbitrary choice was made μ0 = 4π × 10 is deﬁned by the current in parallel wires at one meter distance from each other that gives a force of 2 × 10−7 Newtons per meter. and a unit of mass related to the length unit and the mass of water. Coulombs law is not fundamental and the 4π belonged there. The Coulomb is set so that the Ampere is one Coulomb per second. a unit of time approximately equal to the time between heartbeats. but. Maxwell’s Equations in CGS units are ∇·B 1 ∂B ∇×E+ c ∂t ∇·E = 0 = 0 = 4πρ
. With this modiﬁcation.438
31
31. however. None of these depend on any even nearly fundamental physical quantities. The CGS units are not perfect. leaving the force unchanged. We will correct this little mistake and move to Rationalized HeavisideLorentz Units by making a minor modiﬁcation to the unit of charge and the units of ﬁelds. With these choices SI units make Maxwell’s equations and our ﬁled theory look very messy. our ﬁeld theory will have few constants to carry around.1
Classical Maxwell Fields
Rationalized HeavisideLorentz Units
The SI units are based on a unit of length of the order of human size originally related to the size of the earth.
the equations remain the same except the factors of 4π in front of the source terms disappear. c When we change to Rationalized HeavisideLorentz units. For our calculations. We know that Eﬁelds can transform into Bﬁelds and vice versa. c
∇×B− The Lorentz Force is
=
1 F = −e(E + v × B). For example. (which is a Lorentz vector) Aμ = (A. we can set c = 1 any time we want unless we need answers in centimeters. the equations become
∇·B = 0 1 ∂B ∇×E+ =0 c ∂t ∇·E =ρ 1 ∂E 1 ∇×B− = j c ∂t c 1 F = −e(E + v × B) c
That is.2
The Electromagnetic Field Tensor
The transformation of electric and magnetic ﬁelds under a Lorentz boost we established even before Einstein developed the theory of relativity. a point charge at rest gives an Electric ﬁeld.439 1 ∂E c ∂t 4π j.
. it would still be convenient to set c = 1 since this has been confusing us about 4D geometry and c is the last unnecessary constant in Maxwell’s equations. Of course. iφ). If we boost to a frame in which the charge is moving. This means that the Eﬁeld cannot be a Lorentz vector.
Fμν
0 −Bz ⎜ =⎝ By iEx
⎛
Bz 0 −Bx iEy
−By Bx 0 iEz
⎞ −iEx −iEy ⎟ ⎠ −iEz 0
The ﬁelds can simply be written in terms of the vector potential.
31. there is an Electric and a Magnetic ﬁeld. We need to put the Electric and Magnetic ﬁelds together into one (tensor) object to properly handle Lorentz transformations and to write our equations in a covariant way. The simplest way and the correct way to do this is to make the Electric and Magnetic ﬁelds components of a rank 2 (antisymmetric) tensor.
. As before. checking the (old) deﬁnition of the ﬁelds in terms of the potential. lets verify a few terms in the equations. We may write the other two Maxwell equations in terms of the 4vector jμ = (j.
. Lets take some example oﬀdiagonal terms in the ﬁeld tensor. and God said
∂ ∂xν ∂Aν ∂xμ
−
∂Aμ ∂xν
=
jμ c
and there was light. Its right.
∂Fμν jμ = ∂xν c
Which is why the Tshirt given to every MIT freshman when they take Electricity and Magnetism should say “. B E F12 F13 F4i = = = = = ∇×A −∇φ − 1 ∂A c ∂t ∂A2 ∂A1 − = (∇ × A)z = Bz ∂x1 ∂x2 ∂A3 ∂A1 − = −(∇ × A)y = −By ∂x1 ∂x3 ∂(iφ) ∂Ai ∂A4 1 ∂Ai − − = = −i ∂x4 ∂xi ic ∂t ∂xi
1 ∂Ai ∂φ + c ∂t ∂xi
= −i
∂φ 1 ∂Ai + ∂xi c ∂t
= iEi
Lets also check what the Maxwell equation says for the last row in the tensor.”
Of course he or she hadn’t yet quantized the theory in that statement. For some peace of mind. Clearly all the diagonal terms in the ﬁeld tensor are zero by antisymmetry.440
Fμν =
∂Aν ∂Aμ − ∂xμ ∂xν
Note that this is automatically antisymmetric under the interchange of the indices. icρ). ∂F4ν ∂xν ∂F4i ∂xi ∂(iEi ) ∂xi ∂Ei ∂xi ∇·E = = = = = j4 c icρ c iρ ρ ρ
We will not bother to check the Lorentz transformation of the ﬁelds here.. the ﬁrst two (sourceless) Maxwell equations are automatically satisﬁed for ﬁelds derived from a vector potential.
not just the current. As with the scalar ﬁeld. Again. So. That is.3
The Lagrangian for Electromagnetic Fields
There are not many ways to make a scalar Lagrangian from the ﬁeld tensor. not a scalar. The EM interaction is known to conserve parity so this is not a real option. so the simple scalar we can write is jμ Aμ . Of course. ∂ ∂xν ∂L ∂(∂Aμ /∂xν ) − ∂L ∂Aμ = 0 ∂Aν 1 1 1 ∂Aν ∂Aμ ∂Aμ − Fμν Fμν + jμ Aμ = − − − 4 c 4 ∂xμ ∂xν ∂xμ ∂xν ∂Aσ ∂Aσ 1 ∂ ∂Aλ ∂Aλ − − − 4 ∂Aμ /∂xν ∂xλ ∂xσ ∂xλ ∂xσ 1 ∂ ∂Aσ ∂Aλ ∂Aσ ∂Aσ − −2 2 4 ∂Aμ /∂xν ∂xλ ∂xλ ∂xλ ∂xσ ∂Aμ 1 ∂Aν − 4 − 4 ∂xν ∂xμ −Fνμ = Fμν 0 0 jμ c 1 + jμ Aμ c
L = ∂L ∂(∂Aμ /∂xν ) = = = = ∂ ∂L Fμν − ∂xν ∂Aμ ∂ jμ Fμν − ∂xν c ∂ Fμν ∂xν = = =
.441
31. The next step is to check what the EulerLagrange equation gives us. We already know that ∂Fμν jμ = ∂xν c and we need to make our Lagrangian out of the ﬁelds. The Lagrangian for Classical Electricity and Magnetism we will try is. we will treat each component of A as an independent ﬁeld. the only reasonable choice is r Fμν Fμν = 2(B 2 − E 2 ). we need to add an interaction with a source term. it changes sign under a parity transformation. The source of the ﬁeld is the vector jμ . we know electromagnetism well. so ﬁnding the right Lagrangian is not really guess work. Also we want a linear equation and so higher powers of the ﬁeld should not occur. One might consider eμνλσ Fμν Fλσ = B · E but that is a pseudoscalar.
1 1 LEM = − Fμν Fμν + jμ Aμ 4 c
In working with this Lagrangian. xμ cannot appear explicitly because that violates symmetries of nature. A term of the form mAμ Aμ is a mass term and would cause ﬁelds to fall oﬀ faster than 1 .
The EulerLagrange equation gets us back Maxwell’s equation with this choice of the Lagrangian.
H
= Fμ4 F4μ + = = = =
∂A4 1 + Fμν Fμν ∂xμ 4 ∂A4 1 −F4μ F4μ + + Fμν Fμν ∂xμ 4 1 ∂A4 −F4μ F4μ − F4μ + Fμν Fμν ∂xμ 4 ∂A4 1 2 E 2 − F4i + (B − E 2 ) ∂xi 2 1 2 ∂(iφ) (E + B 2 ) − iEi 2 ∂xi
. since we have four independent components of Aμ as independent ﬁelds. We could not treat each component of Fμν as independent since they are clearly correlated. Using the 4vector potentials as the ﬁelds does give the right answer. This clearly justiﬁes the choice of L. We use the standard deﬁnition of the Hamiltonian in terms of the Lagrangian. Electricity and Magnetism is a theory of a 4vector ﬁeld Aμ .442 Note that. It is important to emphasize that we have a Lagrangian based. We could have tried using the six independent components of the antisymmetric tensor but it would not have given the right answer. formal classical ﬁeld theory for electricity and magnetism which has the four components of the 4vector potential as the independent ﬁelds. we can check what this Hamiltonian density gives us in a region with no sources. we have four equations. that is. the Hamiltonian density in regions with no source term. or one 4vector equation. In the meantime. We can also calculate the free ﬁeld Hamiltonian density. H= ∂L ∂(∂Aμ /∂dt) ∂Aμ −L= ∂dt ∂L ∂(∂Aμ /∂x4 ) ∂Aμ −L ∂x4
We just calculated above that ∂L = Fμν ∂(∂Aμ /∂xν ) which we can use to get ∂L ∂(∂Aμ /∂x4 ) H = Fμ4 = (Fμ4 ) ∂Aμ −L ∂x4 ∂Aμ 1 + Fμν Fμν = Fμ4 ∂x4 4
H = Fμ4
∂Aμ 1 + Fμν Fμν ∂x4 4
We will use this to quantize the ﬁeld once we have written the radiation ﬁeld in a convenient form.
Maxwell’s equation is ∂Fμν jμ = ∂xν c ∂Aν ∂Aμ jμ − = ∂xμ ∂xν c
∂ ∂xν
∂ ∂Aν ∂ 2 Aμ jμ − = ∂xν ∂xμ ∂x2 c ν 2 ∂ ∂Aν jμ ∂ Aμ − =− ∂x2 ∂xμ ∂xν c ν We can simplify this basic equation by setting the gauge according to the Lorentz condition. Recall that the gauge symmetry of Electricity and Magnetism and the phase symmetry of electron wavefunctions are really one and the same. One point to note is that. This was only a check that the Hamiltonian density in the radiation ﬁeld made sense for Electromagnetism as we know it. we do want to use gauge invariance to simplify our equations. the energy density and an EM ﬁeld. with our choice to “treat each component of Aμ as an independent ﬁeld”. Until then. (Note that the radiation Eﬁeld is produced by a changing Bﬁeld and vice versa. (Remember √ the ﬁelds have been decreased by a factor of 4π compared to CGS units.3).) We will study the interaction between electrons and the electromagnetic ﬁeld with the Dirac equation. H= 1 e p+ A 2m c
2
+ eA0
Note that we will try to keep the radiation ﬁeld separate from the strong static ﬁeld of the atomic nucleus.
31. 2
This is the result we expected. We will not go over the consequences of gauge invariance again here.) We can therefore drop this term and are left with H= 1 2 (E + B 2 ).4
Gauge Invariance can Simplify Equations
We have already studied many aspects of gauge invariance (See Section 19.443 1 2 ∂φ (E + B 2 ) + Ei 2 ∂xi
=
If we integrate the last term by parts. in electromagnetism and the corresponding invariance under a phase transformation in Quantum Mechanics. the Hamiltonian used for nonrelativistic quantum mechanics will be suﬃcient to study interactions between a charge and the radiation ﬁeld. (and the ﬁelds fall to zero at inﬁnity). The Eﬁeld given by the scalar potential is due to charges.
. not really a theory for the ﬁeld Fμν . Neither the phase of the wavefunction nor the vector potential are directly observable. then that term contains a ∇ · E which is zero with no sources in the region. but. we are making a theory for the vector ﬁeld Aμ with a gauge symmetry. but the symmetry is.
31. We will use a further gauge condition in the next chapter to work with transverse ﬁelds. show that the two Maxwell equations with sources 1 are given by the Euler LaGrange equation for the LaGrange density LEM = − 4 Fμν Fμν + 1 jμ Aμ . Bx .444
∂Aν =0 ∂xν
The gauge transformation needed is Aμ → Aμ + 2Λ = − ∂Aν ∂xν ∂Λ ∂xμ
old
The Maxwell equation with the Lorentz condition is now a simple wave equation for the vector potential.
. Az . ∂x 2. Working in Rationalized HeavysideLorentz units. Ez . The second derivative of Λ is set by the Lorentz condition but there is still freedom in the ﬁrst derivative which will modify A. show that the two sourceless Maxwell equations are satisﬁed if the Field Tensor is derived from the vector potential according to the equation ∂Aμ ν Fμν = ∂Aμ − ∂xν with the 4vector potential given by Aμ = (A. Working in Rationalized HeavysideLorentz units. for a boost in the z direction. Gauge transformations can be made as shown below. Use the Lorentz transformation of the 4vector Aμ to derive the Lorentz tranformation of Ax . Use the Lorentz transformation of the tensor Fμν to derive the Lorentz tranformation of Ex . c 3.5
Homework Problems
1.
2Aμ = −
jμ c
There is still substantial gauge freedom possible. and Bz . iφ). 4. Aμ → Aμ + ∂Λ ∂xμ 2Λ = 0
This transformation will not disturb the Lorentz condition which simpliﬁes our equation. and φ for a boost in the z direction.
With this separation.
0 If jμ = 0. but it is still useful. the equations we have contain the fourvector Aμ with all the ﬁelds mixed. we can maintain the form of our nonrelativistic Hamiltonian. making one component of a 4vector zero is not a Lorentz invariant way of working. whereas A⊥ gives rise to the EM radiation from moving charges. the static Electric ﬁeld is represented by a scalar potential. In a region in which there are no source terms.) Enrico Fermi showed. and A⊥ is the part of the vector potential which satisﬁes ∇ · A⊥ = 0. jμ = 0 we can make a gauge transformation which eliminates A0 by choosing Λ such that 1 ∂Λ = A0 .1
Quantum Theory of Radiation
Transverse and Longitudinal Fields
In nonrelativistic Quantum Mechanics. we have the Coulomb potential. Note that A and A4 appear nowhere in the Hamiltonian. magnetic ﬁelds by the vector potential. We have to redo the gauge transformation if we move to another frame. It will be convenient to keep this separation between the large static atomic Electric ﬁeld and the radiation ﬁelds. When we quantize the ﬁeld. then we cannot eliminate A0 . c ∂t Since the fourth component of Aμ is now eliminated. in 1930.
H=
j
e 1 p − A⊥ (xj ) 2mj c
2
+
i>j
ei ej + Hrad 4πxi − xj 
where Hrad is purely the Hamiltonian of the radiation (containing only A⊥ ). however. Again. and the radiation ﬁeld also through the vector potential. all E and B ﬁelds as well as electromagnetic waves will be made up of photons. the Lorentz condition now implies that ∇ · A = 0. This separation is not Lorentz invariant. It is useful to be able to separate the E ﬁelds due to ﬁxed charges from the EM radiation from moving charges. In this case we must separate the vector potential into the transverse and longitudinal parts. (For eample. since 2A0 = jc and we are only allowed to make gauge transformations for which 2Λ = 0. This separation allows us to continue with our standard Hydrogen solution and just add radiation. Instead. with
A = ∇ · A⊥ ∇×A = =
A⊥ + A 0 0
. for atoms we work in a frame with the nucleus at rest and the Eﬁeld from the nucleus is all longitudinal.445
32
32. that A together with A0 give rise to Coulomb interactions between particles. We will not derive this result.
t = 0) = √ V
2
ˆ(α) ck. and k form a right handed orthogonal system.α (t) = ck. We decompose the ﬁeld into its Fourier components at t = 0 1 A(x. ky .446 We will now study the radiation ﬁeld in a region with no sources so that ∇ · A = 0. kz .2
Fourier Decomposition of Radiation Oscillators
Our goal is to write the Hamiltonian for the radiation ﬁeld in terms of a sum of harmonic oscillator Hamiltonians.α (t)eik·x + c∗ (t)e−ik·x k. the wave number. ik) = (kx .α (0)e−iωt where ω = kc.α
k α=1
where ˆ(α) are real unit vectors. and ck. We also assume for now that there are no sources inside the region so that we can make a gauge transformation to make A0 = 0 and hence ∇ · A = 0. The ﬁrst step is to write the radiation ﬁeld in as simple a way as possible. We will work in a cubic volume V = L3 and apply periodic boundary conditions on our electromagnetic waves. t) = √ V
2
d3 xeik·x e−ik ·x = δkk
ˆ(α) ck.α (t = 0)eik·x + c∗ (t = 0)e−ik·x k. the two polarization vectors must be picked so that ˆ(1) . kμ = pμ ω = (kx .α
k α=1
We may write this solution in several diﬀerent ways. 1 A(x. One nice way to write this is in terms 4vector kμ . Once the wave vector is chosen. and use the best one for the calculation being performed. as a sum of harmonic components.α is the coeﬃcient of the wave with wave vector k and polarization vector ˆ(α) . We can now write the vector potential as a function of position and time. The components of the wave vector must satisfy 2πni ki = L due to the periodic boundary conditions. i ) h ¯ c
. ˆ(2) . We know the time dependence of the waves from Maxwell’s equation. The factor out front is set to normalize the states nicely since 1 V and ˆ(α) · ˆ(α ) = δαα . ky . ck. We will use the equations B E ∇2 A − 1 ∂2A c2 ∂t2 = = = ∇×A 1 ∂A − c ∂t 0
32. kz .
α (0)e k α=1
+ c.c.
k α=1 2
= The result here is zero because ˆ(α) · k = 0. just for some practice.c.
1 Aμ = √ V
2 (α) ikρ xρ μ ck.α (0)2e k α=1 2 (α) ikρ xρ μ ck.α
k α=1
A convenient shorthand for calculations is possible by noticing that the second term is just the complex conjugate of the ﬁrst.c. t) = √ V
2
ˆ(α) ck. = 0
The result is zero since kν kν = k 2 − k 2 = 0.
=
+ c. = 0
k α=1
.c.c. t) = √ ˆ(α) ck.c.α (0)eikρ xρ + c∗ (0)e−ikρ xρ k.α (0)eikρ xρ + c.
This choice of gauge makes switching between 4vector and 3vector expressions for the potential trivial.
=
1 √ V 1 √ V
2
ck. Also note that we are working in a gauge with A4 = 0. The unit vectors ˆ(α) are transverse to the direction of propagation.c.
=
1 √ V 1 √ V
2 (α) ikρ xρ μ ck. V k α=1 1 A(x. Its most convenient to use the covariant form of the equation and ﬁeld.c.α (0)(−kν kν )e k α=1
+ c.α (t)ˆ(α) · ∇eik·x + c.α (0)eikρ xρ + c. so this can also represent the 4vector form of the potential. Let’s also verify that ∇ · A = 0.α (0)e k α=1
+ c. The Fourier decomposition of the radiation ﬁeld can be written very simply.c. 2Aμ = 0 2 1 √ V
2 (α) ikρ xρ μ ck. Let’s verify that this decomposition of the radiation ﬁeld satisﬁes the Maxwell equation.
k α=1
Note again that we have made this a transverse ﬁeld by construction. 1 A(x. t) = √ V
2
ˆ(α) ck.α (t)ˆ(α) · keik·x + c.α (t)e
ik·x
+ c. 2 1 A(x. We can then write the radiation ﬁeld in a more covariant way.447 so that kρ xρ = k · x = k · x − ωt.
ick. ∇· 1 √ V
2
ˆ
k α=1
(α)
ck.
We have already calculated the Hamiltonian density for a classical EM ﬁeld. (Note that this simpliﬁcation is possible because we have assumed no sources in the region.α (0)eikρ xρ − c∗ (0)e−ikρ xρ k. Before pulling this all together in a brute force way.
H = Fμ4
∂Aμ 1 + Fμν Fμν ∂x4 4
H = H =
∂A4 ∂Aμ ∂Aμ 1 ∂Aν ∂Aμ − + − ∂xμ ∂x4 ∂x4 4 ∂xμ ∂xν ∂Aμ ∂Aμ 1 ∂Aν ∂Aν ∂Aν ∂Aμ − + − ∂x4 ∂x4 2 ∂xμ ∂xμ ∂xμ ∂xν
∂Aμ ∂Aν − ∂xμ ∂xν
Now lets compute the basic element of the above formula for our decomposed radiation ﬁeld. we can eliminate some terms.)
. its good to realize that almost all the terms will give zero. Going back to our expression for the Hamiltonian density. This is an important calculation because we will use the Hamiltonian formalism to do the quantization of the ﬁeld.α (0)(ikν )eikρ xρ + c∗ (0)(−ikν )e−ikρ xρ k. say kν and to a polarization vector. say μ . We see that the (α) derivative of Aμ is proportional to a 4vector.α ck.α ck.α (0)eikρ xρ − c∗ (0)e−ikρ xρ k. Aμ ∂Aμ ∂xν ∂Aμ ∂xν ∂Aμ ∂x4 = 1 √ V 1 √ V
2 (α) μ k α=1 2 (α) μ k α=1 2 (α) μ kν k α=1 2 (α) ω μ
ck. The dot products of the 4vectors. We will do the calculation using the covariant notation (while Sakurai outlines an alternate calculation using 3vectors).α (0)eikρ xρ + c∗ (0)e−ikρ xρ k.448
32.α
=
1 = i√ V 1 = −√ V
k α=1
c
We have all the elements to ﬁnish the calculation of the Hamiltonian. H H H = = = − ∂Aμ ∂Aμ 1 ∂Aν ∂Aν ∂Aν ∂Aμ + − ∂x4 ∂x4 2 ∂xμ ∂xμ ∂xμ ∂xν ∂Aμ ∂Aμ 1 − + (0 − 0) ∂x4 ∂x4 2 ∂Aμ ∂Aμ − ∂x4 ∂x4
The remaining term has a dot product between polarization vectors which will be nonzero if the polarization vectors are the same.α ck. either k with itself or k with are zero.α (t).3
The Hamiltonian for the Radiation Field
We now wish to compute the Hamiltonian in terms of the coeﬃcients ck.
4
Canonical Coordinates and Momenta
We now have the Hamiltonian for the radiation ﬁeld. is the integral of the Hamiltonian density.α
This is the result we will use to quantize the ﬁeld.α c c
2
H
=
−ck.α (t)c∗ (t) + c∗ (t)ck. It should not be a surprise that the terms that made up the Lagrangian gave a zero contribution because L = 1 (E 2 − B 2 ) and we know that E and B have the same magnitude in a radiation ﬁeld.α (t) k.α k. H= d3 x H
When we integrate over the volume only products like eikρ xρ e−ikρ xρ will give a nonzero result.α (0) eikρ xρ − c∗ (0) e−ikρ xρ k.α (t)c∗ (t) − c∗ (t)ck.α (t)c∗ (t) + c∗ (t)ck. We have been careful not to commute c and c∗ here in anticipation of the fact that they do not commute.α
ω c
2
ck. So when we multiply one sum over k by another.α (t)c∗ (t) + c∗ (t)ck.α k.α k.α (0) eikρ xρ − c∗ (0) e−ikρ xρ k.α
k α=1 2
H H
=
k α=1
ω c
ck.449 The total Hamiltonian we are aiming at.α (t) k. basically because the waves with diﬀerent wave number are orthogonal.α (t) k.
H=
k.α c c
d3 x d3 x
2
∂Aμ ∂Aμ ∂x4 ∂x4 1 V ω c
2 2
k α=1 2
ω ω ck. only the terms with the same k will contribute to the integral. 1 V d3 x eikρ xρ e−ikρ xρ = δkk
H H ∂Aμ ∂x4 H H
= = = = = −
d3 xH ∂Aμ ∂Aμ ∂x4 ∂x4
2 (α) μ k α=1
1 −√ V − − −
ω ω ck.α (t) k.α
=
k.α
ω c
2
ck. 2
32.α k.α
.
α
k.α k.α + c∗ ) k. Lets deﬁne ck.α = − iω (ck. H=
k.α − c∗ )2 + k.α k. The simplest choice for a real coordinates is c + c∗ . With a little eﬀort we can identify the coordinate 1 Qk.α k.α
ω c
2
ck.α − c∗ ).α
This veriﬁes that this choice gives the right Hamiltonian.α
2
k.α k.α c and its conjugate momentum for each oscillator. The position and momentum became operators which did not commute.α c 2 ω (ck.α + c∗ ) k.α + c∗ )2 k.α − c∗ )2 + (ck.450 It was with the Hamiltonian that we ﬁrst quantized the nonrelativistic motion of particles.α c
ω2 (ck.α
ω c
2
2
(ck.α c
.α
ck.α + c∗ ) = k.α c∗ + c∗ ck. k.α c
The Hamiltonian can be written in terms of these. H = = = = =
k.α + ω 2 Q2 k. We wish to write the Hamiltonian in terms of a coordinate for each oscillator and the conjugate momenta. ck.α + c∗ )2 k.α ¨ We can then simplify our notation a bit.α
1 2 1 2 1 2 1 2
2 Pk. one oscillator for each wave vector and polarization.α iω (ck.α + c∗ ) = k.α = −ω 2 ck.α
−
k. The coordinate should be real so it can be represented by a Hermitian operator and have a physical meaning.α to be the time dependent Fourier coeﬃcient.α k.α = (ck.α − iωc∗ ) k.α
This now clearly looks like the Hamiltonian for a collection of uncoupled oscillators.α c iω (−iωck. The ﬁrst equation is ∂H ∂Qk.α c∗ + c∗ ck.α c 2 ω (ck.α k.α k. We should also check that this choice of coordinates and momenta satisfy Hamilton’s equations to identify them as the canonical coordinates.α k.α − c∗ ) ˙ ˙k.α ω 2 Qk.α c∗ + c∗ ck.α 2 ck.α = = ˙ −Pk. Pk.α
ω c
2
(ck.α
ω c ω c ω c
2
−(ck.
Dirac proposed that the canonical variables of the radiation oscillators be treated like p and x in the quantum mechanics we know.α + iωc∗ ) k. For example [px .α + ω Qk.451 This one checks out OK.α .5
Quantization of the Oscillators
To summarize the result of the calculations of the last section we have the Hamiltonian for the radiation ﬁeld.α =
k.α k. neither do the c and c∗ so we should continue to avoid commuting them.α − c∗ ) k. We will impose the same rules here. Diﬀerent coordinates commute with each other as do diﬀerent momenta. so we have identiﬁed the canonical coordinates and momenta of our oscillators.α − c∗ ) = k.α c
This also checks out.α + c∗ ) k.α
Soon after the development of nonrelativistic quantum mechanics.α c iω Pk. x] = h .
.α + c∗ ) ˙ ˙k. We have a collection of uncoupled oscillators with identiﬁed canonical coordinate and momentum.α ] = [Qk. The next step is to quantize the oscillators.α c 1 2 2 2 Pk.α c∗ + c∗ ck.α
1 (ck.
32. Coordinates and momenta that do not correspond. Pk .α c 1 (−iωck.α
ω c
2
ck. x] = 0.α 1 (ck.α c iω − (ck.α . Pk . do commute.α − = = ˙ Qk.α Pk. Qk .α = − (ck.α c
iω (ck.α k.α − c∗ ) = k. The other equation of Hamilton is ∂H ∂Pk. [Qk. The coordinate and its corresponding momentum do not ¯ commute.α .α c iω − (ck.α H= 2 Qk.α ] = [Pk.α ] = i¯ δkk δαα h 0 0
By now we know that if the Q and P do not commute.
H=
k. The place to start is with the commutators. i For example [py .α − c∗ ) k.
α )] = [√ 2¯ ω h 2¯ ω h 1 [ωQk.α + )) k.α + k. [ak.α + k.α ) = H 2 √
h ¯ω
H=
a† ak.α − iPk. including the commutator with
.α 1 2 1 2 = = 1 (ωQk.α 1 1 (ωQk.α
1 2
h ¯ω
This is just the same as the Hamiltonian that we had for the one dimensional harmonic oscillator.α . ak. a† k.α ) 2¯ ω h 1 (ωQk. as we had k.α ] = δkk δαα k (Note that all of our commutators are assumed to be taken at equal time.α .α + iωQk.α − iω(Qk.α ] = 2¯ ω h 1 (−iω[Qk. a† ] = 1. a† .α .α + iPk.α − iPk.α ) 2¯ ω h 1 √ (ωQk.α ] + iω[Pk.α a† ak. everything we know about the raising and lowering operators (See section 9.α − iPk.) The Hamiltonian is written in terms a and a† in the same way as for the 1D harmonic oscillator.α − iωPk. we get ak. Following the same idea.α Pk.α ) k.α + iPk.α ) 2¯ ω h 1 2 (ω 2 Q2 + Pk.α 2¯ ω h i 1 2 2 2 (ω Qk.α )(ωQk.α + iPk.α . Pk.α k. ωQk.α − ¯ ω) h 2¯ ω h 1 2 (ω 2 Q2 + Pk.α = = = = = = a† ak.α ]) = 2¯ ω h 1 (¯ ω + hω) h ¯ = 2¯ ω h = 1
So these are deﬁnitely the raising and lowering operators.α Qk.α a† ak. we want to ﬁnd the analog of the raising and lowering operators. as long as [ak.452 Since we are dealing with harmonic oscillators.α for the 1D harmonic oscillator.α ) k. Of course the commutator would be zero if the operators were not for the same oscillator.α 2¯ ω h 1 2 2 2 (ω Qk. We therefore have the raising and lowering operators.3) applies here.α + k.α + Pk. √ (ωQk.α Pk.α a† k.α + iωQk. We developed the raising and lowering operators by trying to write the Hamiltonian as h H = A† A¯ ω. Therefore. Qk.α .α Pk.α ).α 2¯ ω h h ¯ 1 2 (ω 2 Q2 + Pk.α − iPk.α .α + Pk.α + iPk.
α − 1 a† nk.α k.α = √ (ωQk. √ ak.α c iω Pk.α =
h ¯ c2 ak.α c c 2¯ ω h 1 ω ((ck. 1 ak. H Nk. we also can deﬁne the number operator.α − c∗ )) = √ k. it is clear that these coeﬃcients have themselves become operators.α − c∗ )) k.α + c∗ ) + (ck.α + 1 2 h ¯ω
The last step is to compute the raising and lowering operators in terms of the original coeﬃcients.α + c∗ ) k.α 2ω
Similarly we can compute that
c∗ = k.α + c∗ + ck.α + 1
The nk. As with the 1D harmonic oscillator.α k.α c 1 1 iω ak.α a† ak.α + iPk.α = − (ck.α h ¯ c2
ck. and even the constants.α + 1 nk.α 2¯ ω c h = = ω (2ck.α k.α − c∗ ) k.α nk.α nk.α 1 2 h ¯ω = Nk.α
h ¯ c2 † a 2ω k.α = (ck.α k.α = √ (ω (ck.α = nk.α k.α = nk.α − c∗ ) = √ k.α + c∗ ) − i (ck.α = = a† ak.
.α 2¯ ω c h 1 ω (ck. the raising and lowering of energy eigenstates.α ) 2¯ c2 h 2ω ck.α + k.α
Since we now have the coeﬃcients in our decomposition of the ﬁeld equal to a constant times the raising or lowering operator.453 the Hamiltonian.α ) 2¯ ω h 1 Qk.α can only take on integer values as with the harmonic oscillator we know.
nki .α So the fact that the creation operators commute dictates that photon states are symmetric under interchange.α a† 0 k.. nki .6
Photon States
It is now obvious that the integer nk.α2 . = nk1 . . In fact. . Since [a† ..αi . We can generate any state we want by applying raising operators to the vacuum state.αi k nki .α ] = 0. nk1 .α 0 = a† . nk1 .
32.α1 . nki .
The ground state for a particular oscillator cannot be lowered.. nk2 .454
32.αi )nki . we can hypothesize that the operators that create fermion states do not commute.α2 .. For example if we want to raise two photons out of the vacuum..7
Fermion Operators
At this point. k. b† } = 0 r r
The states are then antisymmetric under interchange of pairs of fermions. a† ... It is called the occupation number for the state designated by wave number k and polarization ˆ(α) .α2 . We can represent the state of the entire volume by giving the number of photons of each type (and some phases).α1 nk2 . interchanging the photons gives the same state.. The state vector for the volume is given by the direct product of the states for each type of photon.αi !
0
The factorial on the bottom cancels all the
√ n + 1 we get from the raising operators..α is the number of photons in the volume with wave number k and polarization ˆ(α) . if we assume that the operators creating fermion states anticommute (as do the Pauli matrices)..αi . =
i
(a† i .α k k k..α k a† a† . we apply two raising operators.. nk2 . The state in which all the oscillators are in the ground state is called the vacuum state and can be written simply as 0 . b† b† 0 = −b† b† 0 r r r r Its not hard to show that the occupation number for fermion states is either zero or one. .
{b† . .αi . Assume b† and r br are the creation and annihilation operators for fermions and that they anticommute.α1 ..
..
Any multiphoton state we construct is automatically symmetric under the interchange of pairs of photons.. then we can show that fermion states are antisymmetric under interchange.
the energy of the vacuum state has been deﬁned to be zero.α k.α a† + a† ak.α k.α k.α
=
1 2
h ¯ ω ak.α
k.α +
1 2
For our purposes.455
32. we may remove the (inﬁnite) constant energy due to the ground state energy of all the oscillators.α 2ω
2
=
k.α
h ¯ ωNk. most physicists thought it was actually zero due to some unknown symmetry.α h ¯ c2 ak.α 2ω h ¯ c2 † a 2ω k. This type of operator is called a ﬁeld operator or a quantized ﬁeld. At this time.α k.α c∗ + c∗ ck. The operator is parameterized in terms of x and t. physicists have diﬃculty explaining how small the energy density in the vacuum is.α
With this subtraction. It is simply the energy of the vacuum which we may deﬁne as zero. H =
k. One thing that must be done is to cut oﬀ the sum at some maximum value of k.α
A is now an operator that acts on state vectors in occupation number space.α
ω c ω c
2
ck. H 0 = 0
.8
Quantized Radiation Field
The Fourier coeﬃcients of the expansion of the classical radiation ﬁeld should now be replaced by operators.α c∗ k.α
h ¯ ω Nk. Until recent experiments showed otherwise.α k. We do not expect electricity and magnetism to be completely valid up to inﬁnite energy. The energy density of the vacuum is hard to deﬁne but plays an important role in cosmology. Certainly by the gravitational or grand uniﬁed energy scale there must be important corrections to our formulas.α h ¯ c2 1 √ 2ω V kα
(α) μ
ak.α
H=
k.α a† + a† ak. ck. The Hamiltonian operator can also be written in terms of the creation and annihilation operators. Note that the ﬁeld ﬂuctuations that cause this energy density.α k. also cause the spontaneous decay of excited states of atoms. In any case we are not ready to consider this problem.α Aμ → → = h ¯ c2 ak. H=
k.α (t)eik·x + a† (t)e−ik·x k.
momentum.9) is associated with an angular momentum of one. We need not add anything to our theory though.α Ha† 0 = a† H + [H.α ¯ k. transform like a Lorentz vector.
. led to an understanding that radiation is made up of spin1 particles with mass zero.α The energy of single photon state is ¯ ω. All ﬁelds correspond to a particle of deﬁnite mass and spin. The polarization vector.α +
1 2
can really be dropped since the sum is over positive and negative k. k · ˆ(±) = 0. and therefore the vector potential. so we deduce that the photon has spin one. Of course we could equally well use circular polarizations which are related to the linear set we have been using by 1 ˆ(±) = ∓ √ (ˆ(1) ± iˆ(2) ). The photon states are also labeled by one of two polarizations.α The momentum of the single photon state is ¯ k. P = This time the
1 2
1 c
E × B d3 x =
k.α k. These are the transverse mode of the photon. The m = 0 component of the photon is not present in radiation but is important in understanding static ﬁelds. The vector potential has been given two transverse polarizations as expected from classical Electricity and Magnetism. The state for a single photon with a given momentum and polarization can be written as a† 0 . We know that the matrix element of vector operators (See section 28.α k. so it sums to zero. the vector properties of the ﬁeld are already included in our assumptions about polarization.α ¯ k. and mass of a single photon state are as we would expect.456 The total momentum in the (transverse) radiation ﬁeld can also be computed (from the classical formula for the Poynting vector). h E2 mc2 = p2 c2 + (mc2 )2 = (¯ ω)2 − (¯ k)2 c2 = h h h ¯ ω2 − ω2 = 0
So the energy.α
h ¯ k Nk. When a photon is emitted. 2 The polarization ˆ(±) is associated with the m = ±1 component of the photon’s spin. k. selection rules indicate it is carrying away an angular momentum of one.α
h ¯ k Nk. a† ] 0 = 0 + hωa† 0 = hωa† 0 k. The result is two possible transverse polarization vectors in our quantized ﬁeld.α k. The longitudinal part is partially responsible for static E and B ﬁelds.α k.α ¯ k. P =
k. while the transverse part makes up radiation. By assuming the canonical coordinates and momenta in the Hamiltonian have commutators like those of the position and momentum of a particle. We now have a pretty good idea how to quantize the ﬁeld for any particle. We have separated the ﬁeld into transverse and longitudinal parts. h P a† 0 = a† P + [P.α k.α
We can compute the energy and momentum of a single photon state by operating on that state with the Hamiltonian and with the total momentum operator. The mass of the photon can be computed. a† ] 0 = 0 + hka† 0 = hka† 0 ¯ k. that we have so far assumed were linear polarizations.
α = = = i [H. we derived the canonical equation for the time dependence of an operator.α (t) c∗ (t) k.α = = h ¯ c2 ak.457
32. ak. where we know there are no photons. In particular.α .α (t) h h ¯ h ¯ i [H.α = a† ak.α
This means that the creation.α
We can now write the quantized radiation ﬁeld in terms of the operators at t = 0. So we can’t ﬁx the number of photons and know the ﬁelds exactly.α (0)e−iωt a† (0)eiωt k.α ˙ a† ˙ k. ak.α (t)] = (−¯ ω)ak.α (t) = −iωak. they do not commute with the occupation number operators Nk. Fluctuations in the ﬁeld take place even in the vacuum state.α ak. annihilation. B(t)] h ¯ i i [H. d B(t) dt ak.10
Uncertainty Relations and RMS Field Fluctuations
Since the ﬁelds are a sum of creation and annihilation operators. ck.α (t) = a† (t) = k.α (0)eikρ xρ + a† (0)e−ikρ xρ k.α Observables corresponding to operators which do not commute have an uncertainty principle between them.
.6). k. and other operators are time dependent operators as we have studied the Heisenberg representation (See section 10.α
Again. a† (t)] = iωa† (t) k.
1 Aμ = √ V
kα
h ¯ c2 2ω
(α) μ
ak. not the location of a photon.9
The Time Development of Field Operators
The creation and annihilation operators are related to the time dependent coeﬃcients in our Fourier expansion of the radiation ﬁeld.
32. the 4vector xρ is a parameter of this ﬁeld.α 2ω h ¯ c2 † a 2ω k.α k.α h ¯
So the operators have the same time dependence as did the coeﬃcients in the Fourier expansion. The ﬁeld operator is Hermitian and the ﬁeld itself is real.
α 2 h ¯ ω (α) −a† e−ikρ xρ 0 ˆ k. Even the E and B ﬁelds do not commute. Another way to say this is that the commutator is nonzero if the coordinates are simultaneous. 0E · E0 ≈ Δl4 Thus if we can probe short distances.α 2ω h ¯ c2 (α) −ωak. Basically. To get an idea about the size of ﬁeld ﬂuctuations.) The calculation is illustrative even though the answer is inﬁnite.α (0)eikρ xρ + a† (0)e−ikρ xρ k. This is a reasonable result considering causality.
. for example in the vacuum state.α (0)eikρ xρ + ωa† (0)e−ikρ xρ ˆ k. any quantum particle will be spread out over a ﬁnite volume and its the average ﬁeld over the volume that might cause the particle to experience a force. Again. then we ﬁnd that h ¯c . some cut oﬀ in the maximum energy would make sense. the eﬀective size of the ﬂuctuations increases. then take the mean square of the average. By (x )] = ic¯ δ(ds = h (x − x )ρ (x − x )ρ )
There is a nonzero commutator of the two spacetime points are connected by a lightlike vector.α (0)eikρ xρ + a† (0)e−ikρ xρ ˆ k. The eﬀect of these ﬁeld ﬂuctuations on particles is mitigated by quantum mechanics. So we could average the Electric ﬁeld over a volume.α
kα
h ¯ c2 (α) ak. a term proportional to aa† ﬁrst creates one photon then absorbs it giving a nonzero contribution for every oscillator mode. We compute 0E · E0 . we should look at the mean square value of the ﬁeld. In reality. The terms sum to inﬁnity but really its the inﬁnitesimally short wavelengths that cause this.α 2ω
1 1 = −i √ c V = = = = i √ V i √ V 1 V 1 V
kα
kα
h ¯ ω (α) ak.458 Of course the average value of the Electric or Magnetic ﬁeld vector is zero by symmetry. It can be shown that [Ex (x).α 2
kα
kα
h ¯ω 1 2 h ¯ω → ∞
k
(Notice that we are basically taking the absolute square of E0 and that the orthogonality of the states collapses the result down to a single sum.α (0)eikρ xρ − a† (0)e−ikρ xρ ˆ k. E Aμ A E E E0 0E · E0 0E · E0 = − = = 1 ∂A c ∂t 1 √ V kα 1 √ V
h ¯ c2 2ω
(α) μ
ak. If we average over a cubic volume ΔV = Δl3 .
α 2ω μ V
kα
. nk. Of course the Electromagnetic waves of classical physics usually have very large numbers of photons and the quantum eﬀects are not apparent.α with a similar expression for the ﬁnal state. This will just come from the linear term in A. we must sum over all the electrons.α − 1 − mc 1 h ¯ c2 (α) Aμ = √ ak.
Hint = −
e¯ h e2 e A·A− σ·∇×A A·p+ mc 2mc2 2mc
For an atom with many electrons. e A · pψi .1) with the quantized ﬁeld is already in the standard Hamiltonian.459 To make a narrow beam of light. Another version of the uncertainty relation is that ΔN Δφ ≥ 1. The initial state i should include a direct product of the atomic state and the photon state. This interaction Hamiltonian contains operators to create and annihilate photons with transitions between atomic states. H Hint = = = e 2 1 p + A + V (r) 2m c e2 e A·A (p · A + A · p) + − 2mc 2mc2 e e2 − A·A A·p+ mc 2mc2
For completeness we should add the interaction with the spin of the electron H = −μ · B. The ﬁeld is evaluated at the coordinate x which should be that of the electron.11
Emission and Absorption of Photons by Atoms
The interaction of an electron (See section 28. We therefore will need a term in the interaction Hamiltonian that contains on annihilation operator (only).α nHint i = ψn . nk. one must adjust the phases of various components of the beam carefully.α photons of this type in the initial state and that one photon is absorbed.
32.α (0)eikρ xρ + a† (0)e−ikρ xρ k.1). From our previous study of time dependent perturbation theory (See section 27. We then could write i = ψi . we know that transitions between initial and ﬁnal states are proportional to the matrix element of the perturbing Hamiltonian between the states. nHint i . Assume there are nk. where phi is the phase of a Fourier component and N is the number of photons. We will ﬁrst consider the absorption of one photon from the ﬁeld. nk. Lets concentrate on one type of photon for now. A good condition to identify the boundary between classical and quantum behavior is that for the classical E&M to be correct the number of photons per cubic wavelength should be much greater than 1.
α − 1ˆ(α) · p ak.α + 1) 2ω ψn e−ik·r ˆ(α) · pψi eiωt
These give the same result as our earlier guess to put an n + 1 in the emission operator (See Section 28. for the emission of a photon the matrix element is. nk. we derived the same formulas for matrix elements (See Section 28. nk.α (0)eikρ xρ + a† (0)e−ikρ xρ · pψi . nk.α (0) eikρ xρ ψi . nk. nk.α eikρ xρ ψi . nk.1).α − 1 √ mc V e 1 √ mc V e 1 √ m V e 1 √ m V
h ¯ c2 (α) ak. This makes k · r an excellent parameter in which to expand decay rate formulas.α + 1 − mc h ¯ c2 e 1 (emit) √ ψn .α − 1
=
ψn  eik·r ˆ(α) · p ψi e−iωt
Similarly. e A · pψi .α nHint i = − k.α mc V 2ω = − e 1 √ m V h ¯ (nk.α ˆ k.
32.
. nk.α + 1ˆ(α) · p a† (0) e−ikρ xρ ψi .α − 1ˆ(α) · p 2ω h ¯ nk.α 2ω h ¯ ψn . nk. nk.12
Review of Radiation of Photons
In the previous section.α 2ω nk. Γi→n = (2π)2 e2  φn e−ik·r ˆ · pφi 2 δ(En − Ei + hω) ¯ m2 ωV
With the inclusion of the phase space integral over ﬁnal states this became Γtot = e2 (Ei − En ) 2π¯ 2 m2 c3 h dΩp  φn e−ik·r ˆ(λ) · pe φi 2
λ
The quantity k · r is typically small for atomic transitions Eγ = pc = hkc ≈ ¯ 1 2 2 α mc 2 h ¯ r ≈ a0 = αmc α 1 α2 mc ¯ h = kr ≈ 2 ¯ αmc h 2
Note that we have take the full binding energy as the energy diﬀerence between states so almost all transitions will have kr smaller than this estimate. that is zero photons in the initial state. nk.α nHint i = ψn .α 2ω
h ¯ c2 ψn .460
nHint i nHint i
(abs)
= = =
− − − −
e 1 ψn .1) that we had earlier used to study decays of Hydrogen atom states with no applied EM ﬁeld.
k · φn rpe )φi · ˆ(λ)
. For single electron atoms.5). You might ask why split it. Γtot =
3 4αωin rni 2 2 3c
Here rni is the matrix element of the coordinate vector between ﬁnal and initial states.. 0. we can sum over the ﬁnal states with diﬀerent m and get a formula only requires us to do a radial integral. We will attempt to understand the selection rules when we include the ik · r term.
32. The next order term in the expansion of e−ik·r = 1−ik ·r +. higher order processes must be considered. Δ Δm Δs = = = ±1. We previously derived the E1 selection rules (See Section 28. 0.
The general E1 decay result depends on photon direction and polarization. The matrix element is proportional to −i φn (k · r)(ˆ(λ) · pe )φi which we will split up into two terms. will allow other transitions to take place but at lower rates.461 The approximation that e−ik·r ≈ 1 is a very good one and is called the electric dipole or E1 approximation. Γtot = e2 (Ei − En ) 2π¯ 2 m2 c3 h
3 αωin 2πc2
dΩγ  φn e−ik·r ˆ(λ) · pe φi 2
λ
≈
dΩγ
λ
4π 3
∞
2
r
0
3
∗ drRnn
n
Rni
i
dΩY
∗
n mn
z Y10
+
−
x
+i √ 2
y
Y11 +
x
+i √ 2
y
Y1−1 Y
i mi
Summing over polarization and integrating over photon direction. Then.
3 4αωin = 3c2 +1 2 +1 2 +1 ∞ ∗ Rn Rn r3 dr 0 2
Γtot
for
=
+1 −1
The decay rate does not depend on the m of the initial state. it can be pried out of this formula. we get a simpler formula that is quite useful to compute the decay rate from one initial atomic state to one ﬁnal atomic state.12.1
Beyond the Electric Dipole Approximation
Some atomic states have no lower energy state that satisﬁes the E1 selection rules to decay to. The reason is that we will essentially be computing matrix elements of at tensor and dotting it into two vectors that do not depend on the atomic state. If information about angular distributions or polarization is needed. ±1..
(Remember and axial vector is the same thing as an antisymmetric tensor. Its another case of 3 ⊗ 3 = 5S ⊕ 3A ⊕ 1S . r × p. 1 φn [(k · r)(ˆ(λ) · p) + (k · p)(ˆ(λ) · r)]φi 2 = 1 k · φn [rp + pr]φi · ˆ(λ) 2 im 1 φn [H0 . Under rotations of the coordinate axes. The traceless symmetric tensor has 5 components like an = 2 operator. the rotation matrix for the 9 component Cartesian tensor will be block diagonal. 1 [(k · r)(ˆ(λ) · p) − (k · p)(ˆ(λ) · r)] = (k × ˆ(λ) ) · (r × p) 2 The atomic state dependent part of this. e¯ h (k × ˆ(λ) ) · σ 2mc
. This is the separation of the Cartesian tensor into irreducible spherical tensors. We can get total angular momentum quantum numbers 2. So the ﬁrst term is reasonably named the Electric Quadrupole term because it depends on the quadrupole moment of the state. (k · r)(ˆ(λ) · pe ) = 1 1 [(k · r)(ˆ(λ) · p) + (k · p)(ˆ(λ) · r)] + [(k · r)(ˆ(λ) · p) − (k · p)(ˆ(λ) · r)] 2 2
The ﬁrst term is symmetric and the second antisymmetric by construction. Under rotations the 5 component (traceless) symmetric tensor will always rotate into another 5 component symmetric tensor. The interaction of the electron spin with the magnetic ﬁeld is of the same order and should be included together with the E2 and M1 terms.) So this is clearly an = 1 operator and can be expanded in terms of the Y1m . and the trace term has one. rr]φi · ˆ(λ) k· = 2 h ¯ imω k · φn rrφi · ˆ(λ) = − 2
δ
ij This makes the symmetry clear. These are the ones for which we can use the WignerEckart theorem to derive selection rules. It does not change parity and gives us the selection rule. 
n
− i ≤ 2 ≤
n
+
i
The second term dots the radiation magnetic ﬁeld into the angular momentum of the atomic state. is an axial vector and therefore has three components. The antisymmetric tensor has 3 components. 1. the second (antisymmetric) term can be rewritten slightly. The 3 component anti symmetric tensor will rotate into another antisymmetric tensor and the part proportional to the identity will rotate into the identity. Each vector has three components. It can be reduced into three spherical tensors. so it is reasonably called the magnetic dipole interaction. and 0. The tensor we make when we just multiply two vectors together can be reduced into three irreducible (spherical) tensors.
Similarly. Note that it is actually a constant times the orbital angular momentum operator L. The direct product tensor has 9. The ﬁve components of the traceless symmetric tensor can be written as a linear combination of the Y2m . The term proportional to δij gives zero because k · ˆ = 0. Its normal to remove the trace of the tensor: rr → rr − 3 r2 . The ﬁrst term can be rewritten.462 Putting these two vectors together is like adding to = 1 states.
Assume thermal equilibrium is reached. (nk. We can calculate the ratio between the emission and absorption rates per atom:
2
Γemit NB = = NA Γabsorb
(nk.13
Black Body Radiation Spectrum
We are in a position to fairly easily calculate the spectrum of Black Body radiation. The two matrix elements are simple complex conjugates of each other so that when we take the absolute square.α
Be−ik·ri ˆ(α) · pi A
i 2
Aeik·ri ˆ(α) · pi B
i
where the sum is over atomic electrons. Some atomic states.α (ehω/kT − 1)
nk. we may cancel them. such as the 2s state of Hydrogen. Therefore.α + 1) nk. This state can only decay by the emission of two photons.463 Higher order terms can be computed but its not recommended.α
¯ 1 = nk. Be−ik·ri ˆ(α) · pi A = Api · ˆ(α) eik·ri B
∗
= Aeik·ri ˆ(α) · pi B
∗
We have used the fact that k · = 0. While E1 transitions in hydrogen have lifetimes as small as 10−9 seconds. and the 2s state has a lifetime of about 1 of 7 a second.
32.α =
1 ¯ ehω/kT − 1
. From statistical mechanics. cannot decay by any of these terms basically because the 2s to 1s is a 0 to 0 transition and there is no way to conserve angular momentum and parity. Assume there is a cavity with a radiation ﬁeld on the inside and that the ﬁeld interacts with the atoms of the cavity.α + 1) NB ¯ = = ehω/kT NA nk. we have NB e−EB /kT ¯ = −E /kT = ehω/kT NA e A and for equilibrium we must have NB Γabsorb NB NA = = NA Γemit Γemit Γabsorb
We have previously calculated the emission and absorption rates. the E2 and M1 transitions have lifetimes of the order of 10−3 seconds. they are the same. Let’s take two atomic states that can make transitions to each other: A → B + γ and B + γ → A. The matrix elements are closely related.
v. The potentials are given by: A(x. We know that the vacuum energy is inﬁnite according to our quantization of all the modes as harmonic oscillators up to inﬁnite frequency. t) = v sin (k · x − ωt) + . using the wave equations and the Lorentz condition and comment on these. t) = a sin (k · x − ωt) e Φ(x.
32. Assume there are no photons between the plates so that we are dealing with only the energy in the vacuum. the parallel component of the electric ﬁeld must go to zero at the surface. ω. k.14
Homework Problems
1. Calculate the new potentials A and Φ. ω+dω) per unit volume can be calculated by multiplying the number of photons by the energy per photon times the number of modes in that frequency interval and dividing by the volume of the cavity. Work in rationalized HeavysideLorentz units. If the plates are good enough conductors. a superposition of a Coulomb ﬁeld from a stationary point charge at the origin and a timedependent electromagnetic ﬁeld. Some people think that evidence for the vacuum energy can be found in the Casimir Eﬀect. in a ﬁnite volume of space. The time dependent ﬁelds are generated by currents at inﬁnity. Is k perpendicular to A? Make a gauge transformation using χ(x. Then the result for the number of photons above is true for all the radiation modes of the cavity. This will
. we will use a cutoﬀ at high frequency to calculate the diﬀerence between vacuum energies with and without the conducting plates. Because the plates are good conductors. 2h Assume the basic cubic volume of side L for the normal vacuum and square plates of width L in xy and small gap a in the zdirection for the Casimir eﬀect vacuum. Under what condition is the Lorentz condition satisﬁed by the new potentials? Brieﬂy comment on your results: does the presence of a static Coulomb ﬁeld change any results obtained thus far in second quantization of the electromagnetic ﬁeld? 2. A force between parallel conducting plates can be calculated based on how the vacuum energy depends on the distance between plates. The energy in the frequency interval (ω. In that case. waves along the direction between the plates are constrained to have nodes at the surface of the plates so that there are less modes available if the plates are close together than if they are far apart and thus less vacuum energy in the ﬁeld. U (ω)dω = h ¯ω
¯ ehω/kT
−1
2
L 2π
3
4πk 2 dk 1 2π
3
1 L3
U (ω) = 8π
dk k2 ¯ dω ehω/kT − 1 1 8π¯ ω 3 h U (ω) = 3 ¯ c 2π ehω/kT − 1 8π hν 3 dω = 3 hω/kT U (ν) = U (ω) ¯ dν c e −1 h ¯ω
This was the formula Planck used to start the revolution. Consider. t) = vc cos (k · x − ωt). There are no currents. however.464 Now suppose the walls of the cavity are black so that they emit and absorb photons at any energy. x Derive relations between a. each mode has zero point energy of 1 ¯ ω. ω Show that the new A is perpendicular to k.
There are similar waves for nx = 0 or ny = 0 but because the distance L is big. However. E0 = h ¯ cL2 a (2π)3 ke−k/kc d3 k
4 3¯ cL2 akc h .
On the other hand. 2 =1
When the plates are far apart. We will also have the waves in x and y go to zero at the end of the large cavity but this is just for convenient state counting. It may even be experimentally realistic since the conductors will allow penetration of high frequency electric ﬁelds.
∞
h ¯ cL2 2π
dk
nz =1
k
k2 +
n2 π 2 −xk z e + a2
dk
1 2 −xk k e 2
=
h ¯ cL2 2π
dkk 2 e−xk +
1 2
dk k 2 e−xk
. The simple cutoﬀ kc modiﬁes this formula.
∞ ∞
E=
nx . The special case of nz = 0 is important because the plates are close together. This is probably very realistic since new physics due to gravity will aﬀect things at very high energies. we will use a cutoﬀ function e−k/kc to remove the inﬁnity. We will not be able to use the integration for a that direction. a wave with nz = 0 is possible for every nonzero nx and ny . E= h ¯ cL2 2π
∞
dk
nz =1 1 kc
k
k2 +
n2 π 2 1 h ¯ cL2 z + k 2 e−k/kc = 2 a 2 2π
∞
dk
nz =1
k
k2 + k2 +
n2 π 2 1 z + k 2 e−xk a2 2
n2 π 2 z a2
We have replaced dk = E=
k k
by x. the diﬀerence between the two vacuum energies will not depend strongly on the cutoﬀ. we can neglect the special case and integrate to get the total energy in the vacuum.ny ∞
1 h ¯ cL2 h ¯ ωn = 2 (2π)2 =1 k2 + n2 π 2 1 z + a2 2
∞
dkx dky
nz =1
2 2 kx + ky + ∞
n2 π 2 1 z + a2 2 k2 +
2 2 kx + ky
E=
h ¯ cL2 2π
k dk
nz =1
k2 =
h ¯ cL2 2π
dk
nz =1
k
n2 π 2 1 z + k2 a2 2
We now apply the cutoﬀ in the same way. The wave vector for these just points down the gap between the plates. their eﬀect is neglegible.465
z be true for wave numbers in the z direction satisfying kZ = naπ where nz > 0. before the plates are put in then is just a fraction of this.ny
1 h ¯ ωn (nz = 0).ny . compute the vacuum energy E0 =
That wasn’t too hard but we have to be more careful with the case of close plates in which the ﬁrst steps in k are very large since now kz = 2nz π . h ¯ cL2 a E0 = kd3 k (2π)3 For both cases.ny . there is only one polarization possible for this wave. π2
Starting from this expression. Hopefully.nz =1 ∞ ∞
h ¯ ωn +
nx . The total energy is E=
nx . There are two polarizations of all the waves that are zero on the surfaces. the E ﬁeld must be in the z direction lest there be a parallel component of that ﬁeld. L3 h ¯ cL3 E0 = h ωn d3 n = ¯ h ¯ ωn d3 k = kd3 k 3 (2π) (2π)3 (There is a factor of 1 since the n are all positive but the k integral doesn’t require that.) The 8 energy in the volume between the two plates.nz =1
h ¯ ωn +
nx . Now we transform the integral to one over k =
∞ nz =1
and
dk .
. t)] for transverse ﬁelds in a region with no sources.
x=1/kc
E=
1 1 h ¯ cL2 d2 1 + 2π dx2 x eπx/a − 1 2x
2
x=1/kc
4
y Prove that a careful expansion yields eyy = 1 − y + y − 720 + ..466
hcL2 d2 ¯ 2π dx2
Starting from this expression show that E =
1 1 x eπx/a −1
+
1 2x
. This calculation does not have terms due to vacuum ﬂuctuations of the ﬁeld but it is done in standard QED in which these ﬂuctuations are included. This seems to be a clear indication that the energy in vacuum ﬂuctuations of the EM ﬁeld is real and that there must be a very large amount of energy per unit volume of empty space (depending stronly on the cutoﬀ of the theory). Does this mean the vacuum energy density in the EM ﬁeld is really there? Can we just subtract oﬀ the huge energy density or do we need some other physics to cancel it? 3. (You may include −1 2 12 output from mathematica or matlab for this part.. The resulting force does not depend on the cutoﬀ. It gets the same answer as long as α is large enough to make the conductor good enough to exclude ﬁelds well. Bj (x . t). E − E0 =
4 4 π3 3¯ cL2 akc h h ¯ cL2 6akc h ¯ cL2 π 2 − − =− 2π π 360a3 π2 720a3
Compute the force per unit area of the plates.) Using this expansion show 4 ¯ cL2 6akc π3 that E = h2π π − 360a3 . The situation is similar to the force between charged plates: it is the charges that are attracting each other but we can also calculate the force based on the energy stored in the ﬁeld between the plates. This is an attractive force which is only measurable for small separations between the plates. 4 h ¯ cL2 6akc π3 − 2π π 360a3
E=
Now the energy diﬀerence E − E0 is the quantity of interest. This result seems rather important. People have also calculated this force based on currents and charges in the conductors creating images and attracting each other. It has been checked experimentally and is found to be correct to a few percent experimental accuracy. Conducting plates attract each other in order to reduce the energy due to vacuum ﬂuctuations in the space between the plates. Compute the equal time commutator [Ei (x. The calculation in QED must include retardation (speed of light) eﬀects betwee the two plates.
.
Nevertheless this part of the interaction could contribute in second order perturbation theory.α + a† .467
33
Scattering of Photons
In the scattering of photons. The order does not matter. k ˆ(α ) is given
. Aμ (x) e2 n. which is what really counts when e2 expanding in powers of α. Therefore. Any calculation we will do will use the matrix element of the interaction Hamiltonian between initial and ﬁnal states.α a† .α ak. kˆ(α) μ μ k k 2 ωω h ¯ c2 (α) (α ) −i(ω−ω )t √ n.α a† . k ˆ(α ) Hint i. by absorbing one photon in a transition from the initial atomic state to an intermediate state. k ˆ(α )  ak. k ˆ(α )  ak.α ak. The k k
e − mc A · p term has both creation and annihilation operators in it but not products of them. We will assume that the wavelength of the photon’s is long compared to the size of the atom so that eik·r ≈ 1.α (0)eikρ xρ + a† (0)e−ikρ xρ k. While this is higher order in perturbation theory.α
kα
e2 1 2mc2 V e2 1 2mc2 V e2 1 2mc2 V e2 1 2mc2 V e2 1 2mc2 V
h ¯ c2 (α) (α ) √ n. not by zero as required for the scattering process. Hni Hint n. we will need to consider the 2mc2 A · A term in ﬁrst order e and the − mc A · p term in second order perturbation theory to get an order α calculation of the matrix element.α + a† . k ˆ(α ) A · Ai. The atom may remain in the same state (elastic scattering) or it may change to another state (inelastic).α i. then emitting another photon and making a transition to the ﬁnal atomic state.
Start with the ﬁrst order perturbation theory term.α ak. an initial state photon with wavenumber k and polarization ˆ is absorbed by the atom and a ﬁnal state photon with wavenumber k and polarization ˆ is emitted. It changes the number of photons by plus or minus one. kˆ(α) 2mc2 = = = = = = 1 √ V h ¯ c2 2ω
(α) μ
ak. All the terms in the sum that do not annihilate the initial state photon and create the ﬁnal state photon give zero.α which are just what we want.α and ak. The amplitude to be in the ﬁnal state n. k ˆ(α ) μ μ e 2 ωω h ¯ c2 (α) (α ) −i(ω−ω )t √ 2 ni μ μ e 2 ωω h ¯ c2 (α) (α ) −i(ω−ω )t √ δni μ μ e ωω
This is the matrix element Hni (t).α a† . for example from an atom. kˆ(α) μ μ k k 2 ωω h ¯ c2 (α) (α ) √ n.α ei(kρ −kρ )xρ i. it is the same order in the electromagnetic coupling constant e. k ˆ(α ) 2i. kˆ(α) e2 e A·A A(x) · p + = − mc 2mc2 =
The scattering process clearly requires terms in Hint that annihilate one photon and create ane2 other. The 2mc2 A · A is the square of the Fourier decomposition of the radiation ﬁeld so it contains terms like a† .
α 2ω
kα t2 iωnj t2 0
c(2) (t) n
=
−1 h ¯2
dt2 VnI (t2 )e
j. nk. nk . The transition from the initial state to the intermediate state takes place at time t1 . k ˆ(α ) (ˆ(α) ak.α 0
dt1 eiωji t1 VIi (t1 )
c
(2) n. Our notation is that the intermediate state of atom and ﬁeld is called I = j. The transition from the intermediate state to the ﬁnal state takes place at time t2 .k.
t
c(1) (t) n
=
1 i¯ h
0
eiωni t Hni (t )dt
t (α) (α ) μ μ δni 0 t
(1) c n.468 by ﬁrst order time dependent perturbation theory.k ˆ(α
)
(t)
=
−e2 m 2 c2 ¯ 2 h
t2
I
h 1 ¯ c2 √ V 2 ωω
t
dt2 n.k ˆ(α
)
(t) =
h 1 e 2 1 ¯ c2 √ i¯ 2mc2 V ω ω h
eiωni t e−i(ω−ω )t dt
=
e2 √ ˆ(α) · ˆ(α ) δni 2imV ω ω
ei(ωni +ω −ω)t dt
0
Recall that the absolute square of the time integral will turn into 2πtδ(ωni + ω − ω).
Now we very carefully put the interaction term into the formula for second order time dependent perturbation theory.α where j represents the state of the atom and we may have zero or two photons.
. again using eik·x ≈ 1.α e−iωt + a† eiωt k. We will carry along the integral for now. as indicated in the diagram.α .
The spacetime diagram below shows the three terms in cn (t) Time is assumed to run upward in the diagrams.
V
= −
e e 1 √ A·p =− mc mc V
t
h ¯ c2 (α) ˆ · p ak.α e−iωt1 + ˆ(α ) a† . since we are not yet ready to square it. kˆ(α)
We can understand this formula as a second order transition from state i to state n through all possible intermediate states.α eiω k
0 t1
t2
) · pI eiωnj t2
×
0
dt1 eiωji t1 I(ˆ(α) ak.α e−iωt2 + ˆ(α ) a† .α eiω k
) · pi.
k ˆ
(t)
=
−e2 √ 2V m2 ¯ ω ω h e
i(ωnj −ω)t2
dt2 e
j 0
i(ω +ωnj )t2
nˆ · pj jˆ · pi
t2
ei(ωji −ω)t1 i(ωji − ω)
t2 0
⎤ ⎦
+
nˆ · pj jˆ · pi
t
ei(ω +ωji )t1 i(ω + ωji )
0
cn. leaving the atom in an intermediate state which may or may not be the same as the initial (or ﬁnal) atomic state. The operators just give a factor of 1 and make the photon states work out. note that we integrate over the times t1 and t2 and that t1 < t2 . Diagrams (a) and (b) represent two second order terms. leaving the atom in some intermediate state. In diagram (a) the initial state photon is absorbed at time t1 . In diagram (b).k ˆ (t)
(2)
=
−e2 √ 2V m2 ¯ ω ω h
dt2 ei(ω +ωnj )t2 nˆ · pj jˆ · pi
j 0
ei(ωji −ω)t2 − 1 i(ωji − ω)
+
ei(ωnj −ω)t2 nˆ · pj jˆ · pi
ei(ω +ωji )t2 − 1 i(ω + ωji )
. not changing any formulas. The second order formula above contains four terms as written. At time t2 the atom absorbs the initial state photon. The intermediate state I includes two photons in the ﬁeld for this diagram. The aa and a† a† terms will clearly give zero.k ˆ(α
)
(t)
= +
−e2 √ 2V m2 ¯ ω ω h e
i(ωnj −ω)t2
t
t2
dt2
j (α) 0 0
dt1 ei(ω +ωnj )t2 nˆ(α ) · pj jˆ(α) · pi ei(ωji −ω)t1
nˆ
· pj jˆ(α) · pi ei(ω +ωji )t1
t
(2) cn. The a† a and aa† terms are the ones described by the diagram. This intermediate state has no photons in the ﬁeld. Note that we are just picking the terms that will survive the calculation. Looking again at the formula for the second order scattering amplitude. the annihilation operator ak. the second order term reduces to.
(2) c n. For diagram (b) its just the opposite. Now.α is active at time t1 and the creation operator is active at time t2 .469
Diagram (c) represents the A2 term in which one photon is absorbed and one emitted at the same point. For diagram (a). If j is the intermediate atomic state. the atom emits the ﬁnal state photon at time t1 . reduce to the two nonzero terms.
k ˆ
ei(ωni +ω −ω)t2 nˆ · pj jˆ · pi −e2 √ 2iV m2 ¯ ω ω h
t
(t) =
j −ω)t2
1 i(ω + ωji ) nˆ · pj jˆ · pi nˆ · pj jˆ · pi + ωji − ω ω + ωji
×
0
dt2 ei(ωni +ω
We have calculated all the amplitudes.k ˆ
c(1) (t) + c(2) (t) n n e2 √ ˆ · ˆ δni 2iV m ω ω −e2 √ 2iV m2 ¯ ω ω j h ⎛ ⎝δni ˆ · ˆ − 1 m¯ h e2 √ 2iV m ω ω
t t
(t) =
ei(ωni +ω
0
−ω)t
dt
t
(2) cn. cn (t) =
(1) c n. −e2 √ 2V m2 ¯ ω ω h
t
(2) c n. We can anticipate that the integral over t2 will eventually give us a delta function of energy conservation. Those −1 terms can never go to inﬁnity and can therefore be neglected. the whole thing goes to zero. going to inﬁnity when energy is conserved and going to zero when it is not. When the energy conservation is satisﬁed.k ˆ (t) =
j
×
dt2 ei(ωni +ω
0
2
c(t)2
=
1 δni ˆ · ˆ − m¯ h e4 2 m2 ω ω 4V
0 t
j
nˆ · pj jˆ · pi nˆ · pj jˆ · pi + ωji − ω ω + ωji
2 i(ωni +ω −ω)t2
×
dt2 e
2
c(t)2
= ×
1 δni ˆ · ˆ − m¯ h
4
j
nˆ · pj jˆ · pi nˆ · pj jˆ · pi + ωji − ω ω + ωji
e 2πtδ(ωni + ω − ω) 4V 2 m2 ω ω
.470 The −1 terms coming from the integration over t1 can be dropped. The ﬁrst order and second order amplitudes should be combined.k ˆ
(t) =
nˆ · pj jˆ · pi nˆ · pj jˆ · pi + ωji − ω ω + ωji nˆ · pj jˆ · pi nˆ · pj jˆ · pi + ωji − ω ω + ωji
−ω)t2
dt2 ei(ωni +ω −ω)t2
0
⎞ ⎠
cn.k ˆ
(t) =
dt2 ei(ωni +ω −ω)t2 nˆ · pj jˆ · pi
j 0
1 i(ωji − ω)
+ c
(2) n. then squared. those terms are negligible and when it is not.
Even now. The ﬁnal step to a diﬀerential cross section is to divide the transition rate by the incident ﬂux of particles.
2
dσ = dΩ
e2 4πmc2
2
2
ω ω
1 δni ˆ · ˆ − m¯ h
j
nˆ · pj jˆ · pi nˆ · pj jˆ · pi + ωji − ω ωji + ω
This is called the KramersHeisenberg Formula.
2
e4 ω 1 dσ δni ˆ · ˆ − = dΩ (4π)2 m2 c4 ω m¯ h
j
nˆ · pj jˆ · pi nˆ · pj jˆ · pi + ωji − ω ω + ωji
e The classical radius of the electron is deﬁned to be r0 = 4πmc2 in our units. We will factor the square of this out but leave the answer in terms of fundamental constants. the three (spacetime) Feynman diagrams are visible as separate terms in the formula. This is a surprisingly easy step because we are using plane waves of photons.471
2
Γ
= ×
V d3 k 1 δni ˆ · ˆ − (2π)3 m¯ h
4
j
nˆ · pj jˆ · pi nˆ · pj jˆ · pi + ωji − ω ω + ωji
e 2πδ(ωni + ω − ω) 4V 2 m2 ω ω
2
Γ
= ×
1 V ω 2 dω dΩ δni ˆ · ˆ − (2πc)3 m¯ h e4 4V
2 m2 ω
j
nˆ · pj jˆ · pi nˆ · pj jˆ · pi + ωji − ω ω + ωji
ω
2πδ(ωni + ω − ω)
2
Γ
= ×
1 dΩ δni ˆ · ˆ − m¯ h e Vω 2π 3 4V 2 m2 ω ω (2πc)
2 4
j
nˆ · pj jˆ · pi nˆ · pj jˆ · pi + ωji − ω ω + ωji
2
dΓ dΩ
=
e4 ω 1 δni ˆ · ˆ − 2 V m 2 c3 ω (4π) m¯ h
j
nˆ · pj jˆ · pi nˆ · pj jˆ · pi + ωji − ω ω + ωji
Note that the delta function has enforced energy conservation requiring that ω = ω − ωni .
. but we have left ω in the formula for convenience. so the ﬂux is simply V . The initial c state is one particle in the volume V moving with a velocity of c.
These inﬁnities come about because we have not properly accounted for the ﬁnite lifetime of the intermediate state when we derived the second order perturbation theory formula. has unphysical inﬁnities if an intermediate state is on the mass shell. below. These resonances in the cross section can dominate scattering. The energy denominators in the formula suppress larger energy nonconservation. for the very short time that the system is in an
intermediate state.) Note that.1
Resonant Scattering
The KramersHeisenberg photon scattering cross section. In fact the cross section will be large but not inﬁnite when energy is conserved in the intermediate state. the cross section becomes large but not inﬁnite. as we will attempt below. energy conservation is not strictly enforced.
2
dσ = dΩ
e2 4πmc2
2
ω ω
1 δni ˆ · ˆ − m¯ h
j
nˆ · pj jˆ · pi nˆ · pj jˆ · pi + ωji − ω ωji + ω
In reality. the cross section is large but not inﬁnite. Also note that the formula yields an inﬁnite result if ω = ±ωji . This is not a physical result. Again both resonant terms in the cross section.
33. occur if an intermediate state has the right energy so that energy is conserved.472
2
(They show up like c +
j
(a + b) . If the energy width of the intermediate states is included in the calculation.
. The formula can be applied to several physical situations as discussed below. This condition is often refereed to as “the intermediate state being on the mass shell” because of the relation between energy and mass in four dimensions. The resonance in the cross section will exhibit the same shape and width as does the intermediate state.
x] = h ¯ (ˆ · p)ij im (ˆ · x)ij i¯ ˆ · ˆ h = = = = =
j
=
j
ˆ· ˆ
Ei −Ej h ¯
=
−1 m¯ h
j
(Reminder: ωij =
is just a number.)
. xi pj − pj xi = i¯ δij h The commutator of the vectors is i¯ times the identity. (ˆ · p)ij = iˆ · pj is a matrix element between states. dσelastic = dΩ e2 4πmc2
2 2
1 δii ˆ · ˆ − m¯ h
j
iˆ · pj jˆ · pi iˆ · pj jˆ · pi + ωji − ω ωji + ω
With the help of some commutators. then use the commutator with H to change x to p. 1 =
j
ij
ji
i¯ ˆ · ˆ h
=
j
[(ˆ · x)ij (ˆ · p)ji − (ˆ · p)ij (ˆ · x)ji ] h ¯ p im (ˆ · [H. as are the initial and ﬁnal photon energies. the δii term can be combined with the others. The commutator [x. When the two vectors are multiplied directly. p] (with no dot products) can be very useful in calculations. xi pj − pj xi ˆ· ˆ i¯ ˆ · ˆ h = i¯ δij h = ˆi ˆj δij = ˆi ˆj (xi pj − pj xi ) = (ˆ · x)(ˆ · p) − (ˆ · p)(ˆ · x)
Now we need to put the states in using an identity. x])ij hωij (ˆ · x)ij ¯ −i (ˆ · p)ij mωij −i −i (ˆ · p)ij (ˆ · p)ji − (ˆ · p)ij (ˆ · p)ji mωij mωji j −i −i (ˆ · p)ij (ˆ · p)ji + (ˆ · p)ij (ˆ · p)ji mωij mωij −i [(ˆ · p)ij (ˆ · p)ji + (ˆ · p)ij (ˆ · p)ji ] mωij 1 [(ˆ · p)ij (ˆ · p)ji + (ˆ · p)ij (ˆ · p)ji ] ωij
[H.473
33. we get something with two Cartesian indices. This can be used to cast the ﬁrst term above h into something like the other two.2
Elastic Scattering
In elastic scattering. the initial and ﬁnal atomic states are the same.
it useful to again use the commutator to change p into x.3
Rayleigh Scattering
Lord Rayleigh calculated low energy elastic scattering of light from atoms using classical electromagnetism. so the scattering of visible light with be proportional to ω 4 .
. If computation of the matrix elements is planned. Atoms with intermediate states in the visible will appear to be colored due to the strong resonances in the scattering. ∓ωji ωji ± ω dσelas dΩ = ∓ωji ω ω = ∓(1 ∓ ) = ∓1 + ω ωji (1 ± ωji ) ωji ωji e2 4πmc2 e2 4πmc2
2 2
=
mω h ¯ mω h ¯
2 j 2 j
ωji iˆ · xj jˆ · xi ωji iˆ · xj jˆ · xi − ωji − ω ωji + ω [( iˆ · xj jˆ · xi − iˆ · xj jˆ · xi )
2
2
=
+ e2 4πmc2
2
ω ( iˆ · xj ωji 1 ( iˆ · xj ωji
jˆ · xi + iˆ · xj jˆ · xi + iˆ · xj
jˆ · xi )
2
=
m h ¯
2
ω4
j
jˆ · xi )
For the colorless gasses (like the ones in our atmosphere). ω << ωji .474 We may now combine the terms for elastic scattering. then the cross section may be approximated. the ﬁrst excited state in the UV. dσelas dΩ δii ˆ · ˆ 1 1 + ωij ωji ± ω dσelas dΩ = = = e2 4πmc2 −1 m¯ h
2 2
1 δii ˆ · ˆ − m¯ h
j
iˆ · pj jˆ · pi iˆ · pj jˆ · pi + ωji − ω ωji + ω
j
iˆ · pj jˆ · p)i iˆ · pj jˆ · pi + ωij ωij
ωji ± ω + ωij ∓ω = ωij (ωji ± ω) ωji (ωji ± ω) e2 4πmc2
2
=
1 m¯ h
2 j
2
ω iˆ · pj jˆ · pi ω iˆ · pj jˆ · pi − ωji (ωji − ω) ωji (ωji + ω)
This is a nice symmetric form for elastic scattering. which explains why the sky is blue and sunsets are red.
dσelas = dΩ
e2 4πmc2
2
2
mω h ¯
2
ωji
j
iˆ · xj jˆ · xi iˆ · xj jˆ · xi − ωji − ω ωji + ω
33. If the energy of the scattered photon is much less than the energy needed to excite an atom. Rayleigh got the same dependence from classical physics.
In the high energy approximation we have made. dσ = dΩ e2 4πmc2
2 2
ω ω
1 δni ˆ · ˆ − m¯ h
j
nˆ · pj jˆ · pi nˆ · pj jˆ · pi + ωji − ω ωji + ω
The ¯ ω = hω denominators are much larger than nˆ ·pj jˆ·pi which is of the order of the electron’s h ¯ m kinetic energy. both of which must be transverse to the direction of propagation. We have integrated over the ﬁnal state wave vector magnitude. There is no explicit angular dependence but there is some hidden in the dot product between initial and ﬁnal polarization vectors. and is independent of the frequency of the light. if we so choose. there is no dependence on the state of the atoms. we have not integrated over dσ ﬁnal state photon direction yet.4
Thomson Scattering
If the energy of the scattered photon is much bigger than the binding energy of the atom. but. then cross section approaches that for scattering from a free electron. This is a good time to take a look at the meaning of the polarization vectors we’ve been carrying around in the calculation and at the lack of any wavevectors for the initial and ﬁnal state. the initial state wave function will keep these terms small. Alternatively. Set the zaxis to be along the direction of the initial photon and set the xaxis so that the scattered photon is in the xz plane (φ = 0). so we can ignore the second two terms. ˆ(1) · ˆ(1) ˆ ·ˆ ˆ(2) · ˆ(1)
(1) (2)
= cos θ = 0 = 0 = 1
ˆ(2) · ˆ(2)
. ˆ(2) is along the yaxis. A look back at the calculation shows that we calculated the transition rate from a state with one photon with wavevector k and polarization (α) to a ﬁnal state with polarization (α ) .) dσ = dΩ e2 4πmc2
2
ˆ · ˆ 
2
This scattering cross section is of the order of the classical radius of the electron squared. Thomson Scattering. We can compute all the dot products. as indicated by the dΩ . The scattered photon is at an angle θ to the initial photon direction and at φ = 0. We still neglect the eﬀect of electron recoil so we should also require that ¯ ω << me c2 . ω >> 1 eV. we average and/or sum. We are ready to compute four diﬀerent diﬀerential cross sections corresponding to two initial polarizations times two ﬁnal state photon polarizations.475
33. A reasonable set of initial state polarization vectors is ˆ(1) ˆ
(2)
= =
x ˆ y ˆ
Pick ˆ(1) to be in the scattering plane (xz) deﬁned as the plane containing both k and k and ˆ(2) to be perpendicular to the scattering plane. (Even if the intermediate and ﬁnal states have unbound electrons. The only dependence is on polarization. so we are free to choose our coordinate system any way we want. Start from the h KramersHeisenberg formula. subject to the delta function giving energy conservation. ˆ(1) is then at an angle θ to the xaxis.
A given initial photon frequency will produce scattered photons with deﬁnite frequencies. the ﬁnal state can be polarized. Consider the photoelectric eﬀect for the ground state of Hydrogen. At t = 0. A hydrogen atom is in its ground state. the component along ˆ(1) is cos φ and along ˆ(2) is sin φ. we can compute any cross section we want.. For example. cf (t) = δif + λcf (t) + λ2 cf (t) + . dσ = dΩ e2 4πmc2
2
1 (1 + cos2 θ) 2
Even if the initial state is unpolarized. you don’t need to consider states above n = 3. or lines in the spectrum. For simplicity. Calculate the diﬀerential cross section assuming a high energy incident photon and a high energy ﬁnal electron so that electron plane waves are a good approximation for the ﬁnal state.5
Raman Eﬀect
The KramersHeisenberg formula clearly allows for the initial and ﬁnal state to be diﬀerent.6
Homework Problems
1. For a deﬁnite initial state polarization (at an angle φ to the scattering plane. averaging over initial state polarization and summing over ﬁnal is just half the sum of the squares of the above.
33.
(1) (2)
. use time dependent perturbation theory to derive the o amplitude to make a transition from an initial state i to a ﬁnal state f = i to second order in the perturbation λH. Now calculate the transition rate from the 1s to the 3s state and simplify your answer as much as possible. If we don’t observe ﬁnal state polarization we sum (cos θ cos φ)2 + (sin φ)2 and have dσ = dΩ e2 4πmc2
2
1 (cos2 θ cos2 φ + sin2 φ) 2
For atoms with more than one electron. Starting from the Schr¨dinger equation. Of course. all 2 of the above dot products are zero except ˆ(2) · ˆ(2) = 1. total energy is still conserved. this cross section will grow as Z 4 . Calculate the amplitude to be in the 3s state as a function of time in the electric dipole z approximation. for θ = π . The atom changes state and the scattered photon energy is not equal to the initial photon energy.
33. The angular distribution could also be used to deduce the polarization of the initial state if a large ensemble of initial state photons were available.476 From these. For example. That means only the initial photons polarized along the y direction will scatter and that the scattered photon is 100% polarized transverse to the scattering plane (really just the same polarization as the initial state). an oscillating electric ﬁeld is applied: E = λ cos(ωt)ˆ. This is called the Raman eﬀect.. 2.
This calculation will also give us the opportunity to understand resonant behavior in scattering. would have an energy of the order of me c2 . yet as far as we know.
In these. essentially.α ei(k·x−ωt) + a† e−i(k·x−ωt) ˆ k.α
. One can calculate the energy needed to assemble an electron due. Nevertheless. A calculation of the ﬁrst diagram will give the same result for a free electron and a bound electron. Electrons exist and don’t carry inﬁnite amount of energy baggage so we just subtract oﬀ the inﬁnite constant.α 2ω V
k. We can calculate the lowest order self energy corrections represented by the two Feynman diagrams below. a photon is emitted then reabsorbed. Experiments have probed the electron’s charge distribution and found that it is consistent with a point charge down to distances much smaller than the classical radius. we will ﬁnd that the electron’s self energy may change when it is a bound state and that we should account for this change in our energy level calculations. both of these amplitudes are of order e2 . Beyond classical calculations. while the second diagram will give diﬀerent results because the intermediate states are diﬀerent if an electron is bound than they are if it is free. the result is inﬁnite.
Hint
=
−
A =
e A·p mc 1 h ¯ c2 (α) √ ak. As we now know. At this point we must take the unpleasant position that this (constant) inﬁnite energy should just be subtracted when we consider the overall zero of energy (as we did for the ﬁeld energy in the vacuum). The ﬁrst one comes from the A2 term in which the number of photons changes by zero or two and the second comes from the A · p term in second order time dependent perturbation theory. to the interaction of the electron with its own ﬁeld. the self energy of the electron calculated in the quantum theory of Dirac is still inﬁnite but the divergences are less severe. A uniform charge distribution with the classical radius of an electron. We will therefore compute the amplitude from the second diagram. the electron is point charge.477
34
Electron Self Energy Corrections
If one calculates the energy of a point charge using classical electromagnetism.
We separate the terms for absorption and emission and pull out the time dependence.α eiωt
H abs H emit
= =
− −
h ¯ e2 a eik·x p · ˆ(α) 2m2 ωV k.α h ¯ e2 a† e−ik·x p · ˆ(α) 2m2 ωV k. i¯ h dcj dt =
k. We neglect transitions from one intermediate state to another as they are higher order.478 This contains a term causing absorption of a photon and another term causing emission. Hint =
k. We also include the eﬀect that the initial state can become depleted as intermediate states are populated by using cn (instead of 1) in the equation for cj . Transitions through another intermediate state would be higher order and thus should be neglected. Transitions can be made by emitting a photon from ψn to an intermdiate state and transitions can be made back to the state ψn from any intermediate state.
. Recall from earlier calculations that the creation and annihilation operators just give a factor of 1 when a photon is emitted or absorbed. the rate of change of the amplitude to be in a state is given by i¯ h ∂cj (t) ∂t =
k
Hjk (t)ck (t)eiωjk t
In this case.α n abs nHk. j and photon states. We will use the matrix elements of the interaction Hamiltonian between those states. and all intermediate states.α j
dcn i¯ h dt
=
In the equations for cn .α e−iωt + Hk.α abs emit Hk.α j ∗ Hjn
We have dropped the subscript on Hjn specifying the photon emitted or absorbed leaving a reminder in the sum. Note that the matrix elements for the transitions to and from the initial state are closely related. we explicitly account for the fact that an intermediate state can make a transition back to the initial state. and second order perturbation theory will involve a sum over intermediate atomic states.α
The initial and ﬁnal state is the same n .α
Hjn eiωt cn e−iωnj t Hnj e−iωt cj eiωnj t
k. Note also that all the photon states will make nonzero contributions to the sum. From time dependent perturbation theory.) The diﬀerential equations for the amplitudes are then. Hjn Hnj Hnj = = =
emit jHk. ψj plus a photon. ψn . (The diagram is emit a photon from ψn then reabsorb it. we want to use the equations for the the state we are studying.
Previously. cn = e
−iΔEn t h ¯
ΔEn will be a complex number. Note that the double sum over photons reduces to a single sum because we must absorb the same type of photon that was emitted.α
Hjn eiωt cn e−iωnj t e
−iΔEn t h ¯
=
t
cj (t) =
1 i¯ h
k. but needed the assumption that the amplitude to be in the initial state was 1.α 0 t
dt Hjn eiωt e
−iΔEn t h ¯
e−iωnj t
cj (t) =
1 i¯ h
k.α j
Hnj e−iωt cj eiωnj t ei(−ωnj −Δωn +ω)t − 1 h ¯ (ωnj + Δωn − ω) Hnj Hjn e−iωt eiωnj t
k.α
Hjn
Substitute this back into the diﬀerential equation for cn to verify the solution and to ﬁnd out what ΔEn is.) i¯ h dcn dt =
k. i¯ h dcj dt cn =
k. (We have not explicitly carried along the photon state for economy.α 0
dt Hjn ei(−ωnj −Δωn +ω)t ei(−ωnj −Δωn +ω)t h ¯ (ωnj + Δωn − ω) e −1 h ¯ (ωnj + Δωn − ω)
i(−ωnj −Δωn +ω)t t
cj (t) =
k.α j
cj (t) dcn dt
=
k.α j
Hnj 2 ei(ωnj +Δωn −ω)t Hnj 2
k. we did this by integration.α j
ei(−ωnj −Δωn +ω)t − 1 h ¯ (ωnj + Δωn − ω)
ΔEn
=
1 − ei(ωnj +Δωn −ω)t h ¯ (ωnj + Δωn − ω)
Since this a calculation to order e2 and the interaction Hamiltonian squared contains a factor of e2
. the real part of which represents an energy shift. let us make that assumption and plug it into the equations to verify the solution. Since we are attempting to calculate an energy shift.α
Hjn
0
cj (t) =
k. and the imaginary part of which represents the lifetime (and energy width) of the state.479 Our task is to solve these coupled equations.α
Hjn
i¯ h
h = ΔEn e−iΔEn t/¯ =
ei(−ωnj −Δωn +ω)t − 1 h ¯ (ωnj + Δωn − ω)
ΔEn
=
k.
Only photons that satisfy the delta function constraint contribute to the imaginary part. − 2 (ΔEn ) = h ¯
k. h ΔEn =
k.480 we should drop the Δωn = ΔEn /¯ s from the right hand side of this equation.α j
Hnj 2 h ¯ (ωnj − ω) Hnj 2 δ(ωnj − ω) = −π h ¯
k. Moreover. 1 1 − eixt = − iπδ(x) t→∞ x x lim
h h h ¯ Recalling that cn e−iEn t/¯ = e h e−iEn t/¯ = e−i(En +ΔEn )t/¯ . We can relate this width to those we previously calculated. In the upper half plane.α
(ΔEn ) =
−π
k. We will calculate our result in the upper half plane and take the limit as we approach the real axis. there will only be an imaginary part if there is a lower energy state into which the state in question can decay. We have something of the form
t
−i
0
eixt dt =
1 − eixt x
If we think of x as a complex number. the function goes to zero at inﬁnity. x → x + i . our integral goes along the real axis. its not well deﬁned. like the dot product of states with deﬁnite momentum.α j
Hnj 2 δ(En − Ej − ¯ ω) h
j
All photon energies contribute to the real part.α
j
2πHnj 2 h δ(En − Ej − ¯ ω) h ¯
The right hand side of this equation is just what we previously derived for the decay rate of state n. however. the real part of ΔEn corresponds to an energy shift in the state n and the imaginary part corresponds to a width. A little further analysis could show that the second term is a delta function. The second term goes to −∞ there. just above the real axis. summed over all ﬁnal states. 2 − (ΔEn ) = Γn h ¯
.α j
Hnj 2
1 − ei(ωnj −ω)t h ¯ (ωnj − ω)
We have a solution to the coupled diﬀerential equations to order e2 . 1 − eixt = − lim i lim t→∞ →0+ x
∞
eixt dt = lim
0
x 1 = lim 2+ →0+ x + i →0+ x
2
−
x2
i +
2
This is well behaved everywhere except at x = 0. the result oscillates as a function of time. This has been the case for many of our important delta functions.
−iΔEn t
(ΔEn ) =
k. In the lower half plane it blows up at inﬁnity and on the axis. Let us analyze this self energy expression for large time. We should let t → ∞ since the self energy is not a time dependent thing.
c It is valid up to about 2000 eV so we wish to cut oﬀ the calculation around there. t) = ψn (x)e−i(En + (ΔEn ))t/¯ e 2 This also gives us the exponential decay behavior that we expect.α
j
=
e2 2m2 V e (2π)3 2m2
2 2
V d3 k (2π)3
α
j
=
dΩ
α j
=
e 3 2m2 c3 (2π)
dΩ
j α
In our calculation of the total decay rate summed over polarization and integrated over photon direction (See section 28.
ΔEn ≡ (ΔEn ) Hnj H abs ΔEn
=
k. h −Γn t ψn (x. the width just goes into the time dependence as expected and we don’t have to worry about it anymore. The same calculation applies here. While this calculation clearly diverges.α j
Hnj 2 h ¯ (ωnj − ω)
=
abs nHk. Summing these two and integrating over photon direction we got a factor of 8π 3 and the polarization is eliminated from the matrix element. we computed the cosine of the angle between each polarization vector and the (vector) matrix element. Nevertheless. So. keeping resonant scattering cross sections from going to inﬁnity.α j
= − =
h ¯ e2 eik·x p · ˆ(α) 2m2 ωV  neik·x p · ˆ(α) j 2 h ¯ ω(ωnj − ω)  neik·x p · ˆ(α) j 2 ω(ωnj − ω) k 2 dk  neik·x p · ˆ(α) j 2 ω (ωnj − ω) ω neik·x pj · ˆ(α) 2 dω (ωnj − ω)
h ¯ e2 2m2 V
k. For now we will just use it and assume the cutoﬀ is low enough. ΔEn = e2 (2π)3 2m2 c3 e 2 m 2 c3 6π 2α¯ h 3πm2 c2
2 j
8π 3
ω neik·x pj 2 dω (ωnj − ω)
=
j
ω neik·x pj 2 dω (ωnj − ω) ω neik·x pj 2 dω (ωnj − ω)
=
j
Note that we wish to use the electric dipole approximation which is not valid for large k = ω . the largest diﬀerences in corrections between free electrons and bound electrons occur in the region in which the E1 approximation is valid. things are less clear here because of the eventually rapid oscillation of the eik·x term in the integrand as the E1 approximation fails. We can now concentrate on the energy shift due to the real part of ΔEn .7).
.481 The time dependence of the wavefunction for the state n is modiﬁed by the self energy correction.
p For a nonrelativistic free electron the energy 2m decreases as the mass of the electron increases. We will be more interested in accuracy in the next section when we compute the diﬀerence between free electron and bound electron self energy corrections. Since we are still using nonrelativistic quantum mechanics. we will think of this as a renormalization of the electron’s mass.482 It is the diﬀerence between the bound electron’s self energy and that for a free electron in which we are interested. it should be ¯ ω << 2π¯ c/1 = 10keV . The selfenergy due to the interaction of the electron’s charge with its own radiation ﬁeld increases the mass to what is observed.
2
Note that the correction to the energy is a constant times p2 . and hence an increase in the real energy of the electron.
Ecut−of f /¯ h
ΔEf ree
=
2α¯ h p2 3πm2 c2
0
ω dω (ωnj − ω)
Ecut−of f /¯ h
= − = −
2α¯ h p2 3πm2 c2
0
dω
2α¯ h p2 Ecut−of f /¯ h 3πm2 c2 2α p2 Ecut−of f = − 3πm2 c2 = −Cp2 If we were hoping for little dependence on the cutoﬀ we should be disappointed. For h ω the E1 approximation. the cutoﬀ should have ¯ ω << mc2 . The electron starts oﬀ with some bare mass. ΔEf ree = 2α¯ h 3πm2 c2 V 2 ω (ωnj − ω) ω (ωnj − ω)
h h e−ip·x/¯ peip ·x/¯ d3 x 2
dω
2
p
= =
2α¯ h p2 3πm2 c2 V 2 2α¯ h p2 3πm2 c2 V 2 2α¯ h p2 3πm2 c2 2α¯ h p2 3πm2 c2
∞
h h ei(p ·x/¯ −p·x/¯ ) d3 x
dω
p
p
ω V δp .p 2 dω (ωnj − ω)
=
0 ∞
ω dω (ωnj − ω) ω dω → −∞ (ωnj − ω)
=
0
It easy to see that this will go to negative inﬁnity if the limit on the integral is inﬁnite. This self energy calculated is linear in the cutoﬀ. We will approximate (ωnj −ω) ≈ −1 since h h the integral is just giving us a number and we are not interested in high accuracy here. like the nonrelativistic formula
. so the negative sign corresponds to a positive shift in the electron’s mass. The normalized wave function for the free electron is √1V eip·x/¯ . It is quite reasonable to cut oﬀ the integral at some energy beyond which the theory we are using is invalid. we will start with the free electron with a deﬁnite h momentum p. Therefore. Later.
This makes a p2 1 negative energy correction to both the bound (E = − 2n2 α2 mc2 ) and continuum (E ≈ 2m ). Because we ignore the rest energy of the electron in our nonrelativistic calculations. we have already included some of the self energy correction and we must not double correct. It turns out that the relativistic correction diverges logarithmically (instead of linearly) and the diﬀerence between bound and free electrons is ﬁnite relativistically (while it diverges logarithmically for our nonrelativistic calculation).483 for the kinetic energy.3%. the correction to the mass is only about 0. (What p2 would we choose?) Rather me must account for the mass renormalization. In so doing. It makes no sense to trust our nonrelativistic calculation up to inﬁnite energy. its inﬁnite. ≡ = = = = 2α Ecut−of f 3πm2 c2 2 p − Cp2 2mbare 1 − 2C mbare mbare ≈ (1 + 2Cmbare )mbare ≈ (1 + 2Cm)mbare 1 − 2Cmbare 4αEcut−of f (1 + )mbare 3πmc2
C p2 2mobs 1 mobs mobs
If we cut oﬀ the integral at me c2 . then we will be justiﬁed to move the cutoﬀ up to very high energy. We used the observed electron mass in the calculation of the Hydrogen bound state energies. Bound states and continuum states have the same fractional change in the energy.
p2 2mobs
(obs) ΔEn
= =
p2 − Cp2 2mbare ΔEn + C np2 n = ΔEn + 2α Ecut−of f np2 n 3πm2 c2
Because we are correcting for the mass used to calculate the base energy of the state n . We need to add back in a positive term in ΔEn to avoid double counting of the selfenergy correction. particularly if we consider the bound and continuum electron states separately. so we must proceed with the cutoﬀ integral. our correction is written in terms of the electron’s momentum in that state. but if we don’t cut oﬀ. Since the bound state p2 and continuum state terms have the same fractional change. it is convenient to just use 2m for all the corrections. If we use the Dirac theory. Note that the selfenergy of the free electron depends on the momentum of the electron. This is the subtraction we must make.
. Its hard to keep all the minus signs straight in this calculation. so we cannot simply subtract it from our bound state calculation. The free particle correction to the electron mass is positive.
.) This is about the same size as the hyperﬁne splitting of the ground state. Microwave radiation with a (ﬁxed) frequency of 2395 MHz was used to cause transitions to the 2P 3 state and a magnetic ﬁeld was 2 adjusted to shift the energy of the states until the rate was largest. they were able to deduce the shift between the 2S 1 and 2P 1 states. (a wavelength 2 2 of about 30 cm).06 GHz. C. From this. Willis E.484
34. The decay of the 2P 3 2 state to the ground state was observed to determine the transition rate.
The technique used was quite interesting. (The shift is now accurately measured to be 1057. 2 2
Hans Bethe used nonrelativistic quantum mechanics to calculate the selfenergy correction to account for this observation. They made a beam of Hydrogen atoms in the 2S 1 2 state. Retherford used microwave techniques to determine the splitting between the 2S 1 and 2P 1 states in Hydrogen to have a frequency of 1. which has a very long lifetime because of selection rules. Lamb and R.1
The Lamb Shift
In 1947.864 MHz.
we want the cutoﬀ for the calculation to be of order wcut−of f ≈ mc2 /¯ . We will use the E1 approximation and the high h cutoﬀ. it is certainly not warranted for large photon energies. however. At the end. 2α (obs) = ΔEn + C np2 n = ΔEn + Ecut−of f np2 n ΔEn 3πm2 c2 2α¯ h ω neik·x pj 2 dω ΔEn = 2 c2 3πm (ωnj − ω) j ⎞ ωcut−of f ⎛ ω 2α¯ h (obs) ⎝  neik·x pj 2 + np2 n ⎠ dω ΔEn = 3πm2 c2 (ωnj − ω) j
0 ωcut−of f
=
2α¯ h 3πm2 c2
0 ωcut−of f
j
ω  neik·x pj 2 + npj jpn (ωnj − ω) ω  neik·x pj 2 +  npj 2 dω (ωnj − ω)
dω
=
2α¯ h 3πm2 c2
0
j
It is now necessary to discuss approximations needed to complete this calculation. For a good E1 approximation we need Eγ << 1973 eV.)
ωcut−of f (obs) ΔEn
=
2α¯ h 3πm2 c2 2α¯ h 3πm2 c2
j 0 ωcut−of f
ω  npj 2 +  npj 2 dω (ωnj − ω) ω + (ωnj − ω)  npj 2 dω (ωnj − ω)
=
0
j
. the electric dipole approximation will be of great help. On the other hand. as Bethe did. (We aren’t aiming for the worlds best calculation anyway. to get the right answer. In particular. the result from a relativistic calculation can be tacked on to show why it turns out to be the right answer.485
We now can compute the correction the same way he did.
V ] = = = =
h ¯ ∇V i
h ¯ j∇V n i h ¯ npj · j∇V n i j h ¯ i npj j∇V n
j
(Ei − En ) npj jpn
j
This must be a real number so we may use its complex conjugate.
(obs) ΔEn =
2α¯ h log 3πm2 c2
¯ nj  ω ωcut−of f
ωnj  npj 2
j
This sum can now be reduced further to a simple expression proportional to the ψn (0)2 using a typical clever quantum mechanics calculation. We will do the same and pull the log term out as a constant. H0 ]n npj j[p.9α2 mc2 . H0 ]n
j
= [p. We can approximate it by an average. ⎛ ⎞∗ ⎝
j
(Ei − En ) npj jpn ⎠
=
j
(Ei − En ) npj jpn h ¯ i ⎡ n∇V j jpn
j
= −
⎤ npj j∇V n − n∇V j jpn ⎦
(Ei − En ) npj jpn
j
=
h ¯ ⎣ 2i
j
h ¯ = n[p.486
ωcut−of f
= = = ≈ =
2α¯ h − 3πm2 c2 2α¯ h − 3πm2 c2 2α¯ h 3πm2 c2 2α¯ h 3πm2 c2 2α¯ h 3πm2 c2
j
0
ωnj  npj 2 dω ω − ωnj
ω
ωnj [log(ω − ωnj )]0 cut−of f  npj 2
j
ωnj [log(ωnj ) − log(ωcut−of f − ωnj )]  npj 2
j
ωnj [log(ωnj ) − log(ωcut−of f )]  npj 2
j
ωnj log
j
ωnj  ωcut−of f
 npj 2
The log term varies more slowly than does the rest of the terms in the sum. ∇V ]n 2i h ¯2 = − n∇2 V n 2
. Bethe used numerical calculations to determine that the eﬀective average of ¯ ωnj is h 8. The basic Hamiltonian for the Hydrogen atom p2 is H0 = 2m + V (r). H0 ] j[p. [p.
πn3 a3
0
(obs) ΔEn
= − = =
2α¯ h log 3πm2 c2
¯ nj  ω ωcut−of f ωcut−of f ¯ nj  ω ωcut−of f ¯ nj  ω
e2 ¯ 1 h 2 πn3
αmc h ¯
3
α e mc log 3π 2 ¯ n3 h 4α5 mc2 log 3πn3 α5 mc2 log 6π ΔE2s 2π¯ h
(obs)
4 2
ΔE2s
(obs)
= =
mc2 8.9α2 mc2 α5 mc2 c log 12π 2 ¯ c h 1 8.
(obs) ΔEn =
4α5 log 3πn3
ωmin ¯ nj  ω
mc2
4α5 3πn3
log
mc2 2¯ ωnj h¯
+
11 1 − 24 5
mc2
The dependence on ωmin cancels. We only need the nonrelativistic part of the calculation up to photon energies for which the E1 approximation is OK. however. Therefore. The Lamb shift does not depend on the cutoﬀ and hence it is well calculated.487 h ¯2 ne2 δ 3 (x)n 2 e2 ¯ 2 h = − ψn (0)2 2
= −
Only the s states will have a nonvanishing probability to be at the origin with ψn00 (0)2 = 1 h ¯ and a0 = αmc . justiﬁcation in the relativistic calculation. The experimental measurement of the Lamb shift stimulated theorists to develop Quantum ElectroDynamics. the mc2 in the log is the outcome of the relativistic calculation.041 GHz
ν
=
This agrees far too well with the measurement. One may think of the physical origin as the electron becoming less pointlike as virtual photons are emitted
. There is. only the s states will shift in energy appreciably. mc2 4α5 11 1 − log + ΔEn = mc2 3 3πn 2¯ ωmin h 24 5 The nonrelativistic calculation gave. the full calculation was made by using this nonrelativistic approach up to some energy of the order of αmc2 . The relativistic part of the calculation down to ωmin yields. In this calculation. The electric dipole approximation is even pretty good since we did not need to go up to large photon energies nonrelativistically and no E1 approximation is needed for the relativistic part.9α2 = 1. and using the relativistic calculation above that. The relativistic free electron selfenergy correction diverges only logarithmically and a very high cutoﬀ can be used without a problem. The mass of the electron is renormalized as above.
1 The Lamb shift splits the 2S 2 and 2P 1 states which are otherwise degenerate. Its origin 2 is purely from ﬁeld theory. That’s how we (and Bethe) got about the right answer. The correction increases the energy of s states. The shift will be. Typically. considering the approximations made and the dependence on the cutoﬀ. ΔEn = So the sum of the two gives. not the cutoﬀ.
Calculate the Lamb shift for a cutoﬀ of 10 keV instead of the mc2 used by Bethe.005 Angstroms. which can also be calculated in ﬁeld theory. Based on the energy shift. Get a numerical answer.
34.
. right at the origin. Spreading the electron out a bit decreases the eﬀect of being in the deepest part of the potential. makes a small contribution to the Lamb shift.488 and reabsorbed. I estimate that the electron in the 2s state is spread out by about 0. The anomalous magnetic moment of the electron. much more than the size of the nucleus. g − 2.2
Homework Problems
1.
p2 + V (r) E= 2m The natural extension of this is the relativistic energy equation. Both solutions are needed to form a complete set. The KleinGordon equation was indicating that particles of both positive and negative charge are present in the complex scalar ﬁeld. the vector sμ was reinterpreted as the electric current and charge density. so they cannot be discarded. so that’s ﬁne too (using 2 h eimc t/¯ as the time dependence. rather than probability. In an equation that is second order in the time derivative.). It did not take physicists long to come up with this equation. we also need to specify some information about the time derivatives at t = 0 to determine the solution at a later time.
satisﬁes the ﬂux conservation equation ∂sμ h ¯ = ∂xμ 2mi ∂φ∗ ∂φ ∂φ∗ ∂φ + φ∗ 2φ − (2φ∗ )φ − ∂xμ ∂xμ ∂xμ ∂xμ = h ¯ m2 (φ∗ φ − φ∗ φ) = 0 2mi
and reduces to the probability ﬂux we used with the Schr¨dinger equation.
.489
35
35. We may also be motivated to naturally describe particles with spin onehalf. It seemed strange to give up the concept that all information is contained in the wave function to go to the relativistically correct equation. The “negative energy solutions” are needed to form a complete set. The perceived problem with this probability is that it is not always positive. Because the Schr¨dinger equation is ﬁrst order in the time derivative. both positive energies and negative energies are solutions. E 2 = p2 c2 + (mc2 )2 This is just the KleinGordon equation that we derived for a scalar ﬁeld. o The fourth component of the vector is just c times the probability density. He managed to do this but still found “negative energy o solutions” which he eventually interpreted to predict antimatter. the probability density is negative. Later.1
Dirac Equation
Dirac’s Motivation
The Schr¨dinger equation is simply the nonrelativistic energy equation operating on a o wavefunction. Because the energy operator appears squared in the equation. Dirac thought this was a problem. in the nonrelativistic limit. If we have a complex scalar ﬁeld that satisﬁes the (EulerLagrange = KleinGordon) equations 2φ − m2 φ 2φ∗ − m2 φ∗ it can be shown that the bilinear quantity sμ = h ¯ 2mi φ∗ ∂φ ∂φ∗ − φ ∂xμ ∂xμ = = 0 0. With negative energies. Dirac sought to solve the perceived problem by ﬁnding an equation that was somehow linear in the time derivative as is the Schr¨dinger equation. the initial conditions needed o to determine a solution to the equation are just ψ(t = 0).
[σi . Note that this form of the NR Hamiltonian yields the coupling of the electron spin to a magnetic ﬁeld with the correct g factor of 2. The wavefunction now has two components (a spinor) and the eﬀect of spin is included. The spinorbit interaction can be correctly derived from this. t)] c
2
ijk σk . t) + σ · B(r. we showed that the Schr¨dingerPauli o Hamiltonian gives the same result as the nonrelativistic Hamiltonian we have been using and automatically includes the interaction of the electron’s spin with the magnetic ﬁeld. t)]2 − eφ(r. σj }Aj pi + (σi σj + σi σj ) c c ic 2 ∂xi 2 e e e¯ 1 h ∂Aj (σi σj − σj σi + 2δij ) p2 + 2 A2 + 2δij Aj pi + c c ic 2 ∂xi e¯ h e2 2 2e ∂Aj (i ijk σk + δij ) p2 + 2 A + A · p + c c ic ∂xi e¯ h e2 2 2e ∂Aj p2 + 2 A + A · p + i ijk σk c c ic ∂xi e¯ h e2 2 2e p2 + 2 A + A · p + σ · B c c c pi pj +
H H
= =
p2 e e2 e¯ h + A·p+ σ·B A2 − eφ + 2 2m mc 2mc 2mc e 1 e¯ h [p + A(r.490
35. t) 2m c 2mc
We assume the Lorentz condition applies.
and that the momentum
= σi σj = = = = = = =
e2 e Ai Aj + (pi Aj + Ai pj ) c2 c 1 e2 h ¯ ∂Aj e (σi σj + σj σi ) pi pj + 2 Ai Aj + σi σj Aj pi + Ai pj + 2 c c i ∂xi 2 ∂Aj e e¯ h e σi σj δij pi pj + 2 Ai Aj + (σi σj Aj pi + σj σi Aj pi ) + c c ic ∂xi 2 e e e¯ 1 h ∂Aj p2 + 2 A2 + {σi . Recall that {σi .2
The Schr¨dingerPauli Hamiltonian o
In the homework on electrons in an electromagnetic ﬁeld. e σ · [p + A(r. t)
The derivation is repeated here. σj ] = 2 operator diﬀerentiates both A and the wavefunction.
. t)] 2m c
2
− eφ(r. This is a step in the right direction. σj } = 2δij .
H=
e 1 σ · [p + A(r.
Deﬁne φ(L) φ(R) = = φ 1 mc
i¯ h
∂ − i¯ σ · ∇ φ(L) h ∂x0
Including the two components of φ(L) and the two components of φ(R) . we now have four components which satisfy the equations. putting all the terms on one side.491
35. First rewrite the two equations together. ∂ ∂x0 ∂ −i¯ σ · ∇ − i¯ h h ∂x0 i¯ σ · ∇ − i¯ h h φ(L) + mcφ(R) = 0 φ(R) + mcφ(L) = 0
. The idea is to replace p with σ · p.3
The Dirac Equation
We can extend this concept to use the relativistic energy equation (for now with no EM ﬁeld). i¯ h ∂ + i¯ σ · ∇ h ∂x0 i¯ h i¯ h ∂ − i¯ σ · ∇ φ(L) h ∂x0 = (mc)2 φ(L) = (mc)2 φ(L) = mcφ(L) = mcφ(R)
∂ + i¯ σ · ∇ mcφ(R) h ∂x0 ∂ + i¯ σ · ∇ φ(R) h i¯ h ∂x0 ∂ − i¯ σ · ∇ φ(L) h i¯ h ∂x0
These (last) two equations couple the 4 components together unless m = 0. This equation is clearly headed toward being second order in the time derivative. We could continue with this set of coupled equations but it is more reasonable to write a single equation in terms of a 4 component wave function. we can try to write a ﬁrst order equation in terms of a quantity derived from φ. This will also be a ﬁrst order equation. E − p2 = (mc)2 c E + σ · p = (mc)2 c
2
E −σ·p c i¯ ∂ h i¯ ∂ h + i¯ σ · ∇ h − i¯ σ · ∇ φ = (mc)2 φ h c ∂t c ∂t ∂ ∂ + i¯ σ · ∇ h i¯ h − i¯ σ · ∇ φ = (mc)2 φ h i¯ h ∂x0 ∂x0 This is again written in terms of a 2 component spinor φ. Both of the above equations are ﬁrst order in the time derivative. which is ﬁrst order when written in terms of the ﬁeld tensor. As with Maxwell’s equation.
492 Now take the sum and the diﬀerence of the two equations. h i¯ σ · ∇(φ(L) − φ(R) ) − i¯ h ∂ (φ(R) + φ(L) ) + mc(φ(R) + φ(L) ) = 0 ∂x0 ∂ i¯ σ · ∇(φ(R) + φ(L) ) − i¯ h h (φ(L) − φ(R) ) + mc(φ(R) − φ(L) ) = 0 ∂x0
Now rewriting in terms of ψA = φ(R) + φ(L) and ψB = φ(R) − φ(L) and ordering it as a matrix equation. We can rewrite the matrix above as a dot product between 4vectors. the relativistic equation can be simpliﬁed a great deal. h −i¯ σ · ∇(φ(R) − φ(L) ) − i¯ h ∂ (φ(R) + φ(L) ) + mc(φ(R) + φ(L) ) = 0 ∂x0 ∂ i¯ σ · ∇(φ(R) + φ(L) ) + i¯ h h (φ(R) − φ(L) ) + mc(φ(R) − φ(L) ) = 0 ∂x0 ∂ (φ(R) + φ(L) ) − i¯ σ · ∇(φ(R) − φ(L) ) + mc(φ(R) + φ(L) ) = 0 h −i¯ h ∂x0 ∂ i¯ σ · ∇(φ(R) + φ(L) ) + i¯ h h (φ(R) − φ(L) ) + mc(φ(R) − φ(L) ) = 0 ∂x0 ∂ −i¯ h ψA − i¯ σ · ∇ψB + mcψA = 0 h ∂x0 ∂ h ψB + mcψB = 0 i¯ σ · ∇ψA + i¯ h ∂x0 h −i¯ ∂x0 −i¯ σ · ∇ h ∂ ψA ψA + mc =0 ψB ψB i¯ σ · ∇ h i¯ ∂ h
∂x0
Remember that ψA and ψB are two component spinors so this is an equation in 4 components. −i¯ ∂x0 h ∂ −i¯ σ · ∇ h i¯ ∂x0 h ∂ i¯ σ · ∇ h ψA ψB ψ= + mc ψA =0 ψB ⎛ ⎞ ψ1 ⎜ ψ2 ⎟ ≡⎝ ⎠ ψ3 ψ4
ψA ψB
. The matrix has a dot product in 3 dimensions and a time component −i¯ ∂x0 h ∂ −i¯ σ · ∇ h i¯ ∂x0 h ∂ i¯ σ · ∇ h = = h ¯ h ¯ 0 −iσ · ∇ iσ · ∇ 0 0 iσi −iσi 0 + 1 0
∂ ∂x4
0
∂ − ∂x4
0 0 −1
∂ + ∂xi
∂ ∂ = h γμ ¯ ∂x4 ∂xμ
The 4 by 4 matrices γμ are given by. γi γ4 = = 0 iσi 1 0 −iσi 0 0 −1
With this deﬁnition. we get.
A little computation will verify that they anticommute as the Pauli matrices did. That is. γν } = 2δμν . It is interesting to note that the primary physics input was the choice of the Schr¨dingerPauli o Hamiltonian e e [p + A(r. γμ ∂ mc + ∂xμ h ¯ ψ=0
will give the same physical result. t)] c c
.
{γμ . It is easy to see by inspection that the γ matrices are Hermitian and traceless.
0 0 ⎜ γ1 = ⎝ 0 i
⎛
⎞ 0 0 −i 0 −i 0 ⎟ ⎠ i 0 0 0 0 0
0 ⎜ 0 γ2 = ⎝ 0 −1
⎛
0 0 1 0
⎞ 0 −1 1 0 ⎟ ⎠ 0 0 0 0
0 0 ⎜0 0 γ3 = ⎝ i 0 0 −i
⎛
⎞ −i 0 0 i⎟ ⎠ 0 0 0 0
1 ⎜0 γ4 = ⎝ 0 0
⎛
0 1 0 0
⎞ 0 0 0 0 ⎟ ⎠ −1 0 0 −1
Like the Pauli matrices. one for each coordinate but that the row or column of the matrix does not correlate with the coordinate. There are a few other representations of the Dirac matrices that are used.
ψ is a 4component Dirac spinor and. We will try hard to stick with this one. (this time a 4vector). like the spin states we are used to. the one originally proposed by Dirac. This is truly an amazing result. γν } = 2δμν
Sakurai shows that the anticommutation is all that is needed to determine the physics. the gamma matrices form a vector. represents a coordinate diﬀerent from the spatial ones. t)] → σ · [p + A(r. The gamma matrices are 4 by 4 matrices operating in this spinor space. Note that there are 4 matrices.493 ∂ ψ + mcψ = 0 ∂xμ
h ¯ γμ
The Dirac equation in the absence of EM ﬁelds is
γμ
∂ mc + ∂xμ h ¯
ψ = 0. although the representation of ψ may be diﬀerent. for any set of 4 by 4 matrices that satisfy {γμ .
It was Dirac who produced the correct equation for electrons and went on to interpret it to gain new insight into physics. We have applied this same momentum operator relativistically.
. the Schr¨dingerPauli Hamiltonian o was derived from the Dirac equation. Historically.2).494 that gave us the correct interaction with the electron’s spin. but there was no new physics in that since everything could be computed from two components.4
The Conserved Probability Current
We now return to the nagging problem of the probability density and current which prompted Dirac to ﬁnd an equation that is ﬁrst order in the time derivative. We derived the equation showing conservation of probability (See section 6. h φ(R) = i¯ h mc ∂x0 Dirac’s paper did not follow the same line of reasoning. say φ(L) since 1 ∂ − i¯ σ · ∇ φ(L) . ∂t ∂x We also extended it to three dimensions in the same way.
Dirac Biography
35. not much of a stretch.5. t) ∂j(x. t) + = 0. We have also written the equation in terms of four components. for 1D Schr¨dinger theory by using the Schr¨dinger equation o o and its complex conjugate to get an equation of the form ∂P (x.
the adjoint spinor. and subtract. ∂ψ † ∂ψ † mc † ψ =0 γk + γ4 + ∂xk ∂(x4 )∗ h ¯ ∂ψ † ∂ψ † mc † ψ γ4 = 0 γk γ4 − γ4 γ4 + ∂xk ∂x4 h ¯ ∂ψ † γ4 ∂ψ † γ4 mc † ψ γ4 = 0 − γk − γ4 + ∂xk ∂x4 h ¯ ¯ Deﬁning ψ = ψ † γ4 . Start with the Dirac equation.495 Our problem to ﬁnd a similar probability and ﬂux for Dirac theory is similar but a little more diﬃcult. γμ ∂ψ mc ψ=0 + ∂xμ h ¯
∂ψ † mc † ψ =0 γμ + ∂(xμ )∗ h ¯ The complex conjugate does nothing to the spatial component of xμ but does change the sign of the fourth component. − ¯ ¯ ∂ψ ∂ψ γk − γ4 + ∂xk ∂x4 ¯ ∂ψ − γμ + ∂xμ mc ¯ ψ=0 h ¯ mc ¯ ψ=0 h ¯
¯ This is the adjoint equation. we will use the Hermitian conjugate of the Dirac equation instead of the complex conjugate. To turn this back into a 4vector expression. γμ ∂ mc + ∂xμ h ¯ ψ=0
Since the wave function is a 4 component spinor. we can rewrite the Hermitian conjugate equation. The γ matrices are Hermitian. We now multiply the Dirac equation by ψ from the left and multiply the adjoint equation by ψ from the right. ¯ ¯ ∂ψ + mc ψψ + ∂ ψ γμ ψ − mc ψψ = 0 ¯ ¯ ψγμ ∂xμ h ¯ ∂xμ h ¯ ¯ ¯ ∂ψ + ∂ ψ γμ ψ = 0 ψγμ ∂xμ ∂xμ ∂ ¯ ψγμ ψ = 0 ∂xμ ¯ jμ = ψγμ ψ
∂ jμ = 0 ∂xμ
. we can change the sign back by multiplying the equation by γ4 (from the right).
Perhaps we will learn something new though.
35. two components of the Dirac spinor are large and two are quite small. Therefore let us set the properly normalized ∂t conserved 4vector to be
¯ jμ = icψγμ ψ.5.496 We have found a conserved current. we go back to the equations written in terms of ψA and ψB .
35. We know that our nonrelativistic Quantum Mechanics only needed a two component spinor. c ⎞ ⎛ 1 e 2 − c (E + eA0 − mc ) σ · p + cA ⎠ ψA = 0 ⎝ e 1 2 ψB (E + eA0 + mc ) −σ · p + A
c c
e 1 (E + eA0 − mc2 )ψA = σ · p + A ψB c c 1 e 2 (E + eA0 + mc )ψB = σ · p + A ψA c c These two equations can be turned into one by eliminating ψB . Some interpretation will be required as we learn more about the solutions to the Dirac equation and ultimately quantize it. in the nonrelativistic limit. c e e 1 (E + eA0 − mc2 )ψA = σ · p + A σ · p + A ψA c c (E + eA0 + mc2 ) c
. just prior to the introduction of the γ matrices. The fourth component of the current should be ic times the probability density so that the derivative with respect to x4 turns into ∂P . we can write the two component equation that is equivalent to the Dirac equation. We start from the equation in ψA and ψB . We can show that. h Assume that the solution has the usual time dependence e−iEt/¯ . −i¯ ∂x0 h ∂ −i¯ σ · ∇ h i¯ ∂x0 h ∂ i¯ σ · ∇ h σ·p −E c E −σ · p c ψA ψB ψA ψB + mc + mc ψA ψB ψA ψB =0 =0
Turn on the EM ﬁeld by making the usual substitution p → p + e A and adding the scalar potential term. We make the substitution to put the couplings to the electromagnetic ﬁeld into the Hamiltonian. To do this.5
The Nonrelativistic Limit of the Dirac Equation
One important requirement for the Dirac equation is that it reproduces what we know from nonrelativistic quantum mechanics. We may choose an overall constant to set the normalization. Note that we have derived this equation from something that did give the right answers so we expect the Dirac equation to pass this test.1
The Two Component Dirac Equation
First.
so we call ψA the large component 2 and ψB the small component. The one diﬀerence from our understanding of the Dirac equation is in the normalization. When we include relativistic corrections for the ﬁne structure of Hydrogen. we will set A = 0 but have a scalar potential due to the nucleus φ = A0 .5. that is nonrelativistic electrons.. ¯ j0 = ψγ4 ψ = ψ † γ4 γ4 ψ = ψ † ψ
35. ψB would be of order α times smaller. e 1 (E + eA0 + mc2 )ψB = σ · p + A ψA c c c e pc ψB ≈ σ · p + A ψA ≈ ψA 2mc2 c 2mc2 In the Hydrogen atom. ψA is much bigger than ψB . aiming to directly compare to what we have done with the Schr¨dinger equation for Hydrogen. c2 e e σ · p + A ψA σ· p+ A c (E + eA0 + mc2 ) c 2 c σ · pψA σ·p (E + eA0 + mc2 ) = = (E + eA0 − mc2 )ψA (E (N R) + eA0 )ψA
Expand the energy term on the left of the equation for the nonrelativistic case. c2 E + eA0 + mc2 = = = ≈ 1 2m 1 2m 1 2m 1 2m 2mc2 mc2 + E (N R) + eA0 + mc2 2mc2 2mc2 + E (N R) + eA0 1 1+ 1−
E (N R) +eA0 2mc2
E (N R) + eA0 + 2mc2
E (N R) + eA0 2mc2
2
+ . Note that A0 is a function of the coordinates and the momentum operator will diﬀerentiate it.3
The NonRelativistic Equation
Now we will calculate the prediction of the Dirac equation for the nonrelativistic coulomb problem. We shall see below that the normalization diﬀerence is small for nonrelativistic electron states but needs to be considered for atomic ﬁne structure.
35. We will work with the equation for the large component ψA . Remember that the conserved current indicates that the normalization condition for the four component Dirac spinor is.. o As for previous Hydrogen solutions. The energy we have been using in our nonrelativistic formulation is E (N R) = E − mc2 . we must consider the eﬀect ψB has on the normalization. Note that for E ≈ mc2 .497 This is the two component equation which is equivalent to the Dirac equation for energy eigenstates.5.
.2
The Large and Small Components of the Dirac Wavefunction
Returning to the pair of equations in ψA and ψB .
Since this energy term we are expanding is multiplied in the equation by p2 . o we want to isolate the nonrelativistic energy on the right of the equation without other p2 operators. σ·p 1 2m 1− E (N R) + eA0 2mc2 σ · pψA = (E (N R) + eA0 )ψA
The normalization condition we derive from the Dirac equation is
† † ¯ j0 = ψγ4 ψ = ψ † γ4 γ4 ψ = ψ † ψ = ψA ψA + ψB ψB = 1. like the one we used to o calculate the ﬁne structure in Hydrogen. 1− p2 8m2 c2 σ·p 1 2m 1− E (N R) + eA0 2mc2 σ·p 1− p2 8m2 c2 = ψ 1− p2 8m2 c2 (E (N R) + eA0 ) 1 − p2 8m2 c2 ψ
σ · pσ · p p2 σ · pσ · p σ · p E (N R) + eA0 σ · pσ · p p2 − − σ·p− ψ 2m 8m2 c2 2m 2m 2mc2 2m 8m2 c2 p2 p2 p2 = (E (N R) + eA0 ) − E (N R) − eA0 − eA0 2 c2 2 c2 4m 8m 8m2 c2 p2 p2 p2 p2 E (N R) eσ · pA0 σ · p p2 p2 − − − − 2 c2 2m 2 2 c2 2m 8m 2m 2mc 4m 2m 8m2 c2 = (E (N R) + eA0 ) − ψ= ψ
ψ
p4 eσ · pA0 σ · p p2 − − eA0 − 2m 8m3 c2 4m2 c2
p2 p2 p2 E (N R) − eA0 − eA0 2 c2 2 c2 4m 8m 8m2 c2 p2 p2 eA0 − eA0 E (N R) − ψ 8m2 c2 8m2 c2
ψ
.498 We will be attempting to get the correct Schr¨dinger equation to order α4 . pc ψB ≈ ψA 2mc2 pc 2 † † † ψA ψA + ψB ψB ≈ 1 + ψA ψA = 1 2mc2 p2 † ψA ψA = 1 1+ 4m2 c2 p2 ψ ≡ 1+ ψA 8m2 c2 p2 ψA ≡ 1 − ψ 8m2 c2
We’ve deﬁned ψ. but not exactly what we want for the Schr¨dinger equation. we only need the ﬁrst two terms in the expansion (order 1 and order α2 ). the 2 component wavefunction we will use. at least to order α4 . In particular. We can now replace ψA in the equation. We can solve the problem by multiplying both sides of the equation by 1 − 8m2 c2 . σ·p 1 2m 1− E (N R) + eA0 2mc2 σ·p 1− p2 8m2 c2 ψ = (E (N R) + eA0 ) 1 − p2 8m2 c2 ψ
This equation is correct. in terms of ψA so that it is properly normalized.
and now it has. We identify r × p as the orbital angular momentum. The ﬁfth term is the so called Darwin term which we said would come from the Dirac equation.
−eA0 e¯ σ · E × p h Ze2 S · r × p = 2 c2 4m 8πm2 c2 r3 2 e¯ 2 Ze 3 h e¯ ∇ · E h = δ (r) 2 c2 8m 8m2 c2
= −eφ = −e = =
Ze 4πr
Ze2 L · S 8πm2 c2 r3 Ze2 ¯ 2 3 h δ (r) 2 c2 8m
Ze2 p4 h Ze2 L · S Ze2 ¯ 2 3 p2 − − + + δ (r) ψ = E (N R) ψ 3 c2 2 c2 r 3 2 c2 2m 4πr 8m 8πm 8m
This “Schr¨dinger equation”. p2 p4 e¯ σ · E × p − ie¯ E · p − eA0 p2 h h − eA0 − + 3 c2 2m 8m 4m2 c2 = E (N R) − e ψ
h p2 −¯ 2 (∇2 A0 ) + 2i¯ E · p + A0 p2 h − eA0 8m2 c2 8m2 c2 ψ= E (N R) − e h −¯ 2 (∇2 A0 ) + 2i¯ E · p h 2 c2 8m
ψ ψ
p2 p4 e¯ σ · E × p − ie¯ E · p h h − eA0 − + 2 c2 2 c2 2m 8m 4m
p2 p4 e¯ σ · E × p e¯ 2 ∇ · E h h − eA0 − + + 2m 8m3 c2 4m2 c2 8m2 c2
ψ = E (N R) ψ
Ze Now we can explicitly put in the potential due to the nucleus 4πr in our new units. we can cancel several terms. agrees well with the one we o used to understand the ﬁne structure of Hydrogen. derived from the Dirac equation. (The 4π will be absorbed into the new formula for α.
. Now we must simplify two of the terms in the equation which contain the momentum operator acting on the ﬁeld.499 We have only kept terms to order α4 . The ﬁrst two terms are the kinetic and potential energy terms for the unperturbed Hydrogen Hamiltonian. The equation can now be cast in a more familiar form.) The third term is the relativistic correction to the kinetic energy. The fourth term is the correct spinorbit interaction. including the Thomas Precession eﬀect that we did not take the time to understand when we did the NR ﬁne structure. Note that ∇ · E = ρ = Zeδ 3 (r). p2 A0 ψ σ · pA0 σ · p = −¯ 2 ∇2 A0 ψ = −¯ 2 ∇ · ((∇A0 )ψ + A0 ∇ψ) = −¯ 2 ((∇2 A0 )ψ + 2(∇A0 ) · (∇ψ) + A0 ∇2 ψ) h h h = −¯ 2 (∇2 A0 )ψ + 2i¯ E · pψ + A0 p2 ψ h h h ¯ h ¯ σ · (∇A0 )σ · p + A0 σ · pσ · p = − σ · Eσ · p + A0 p2 = i¯ (σi Ei σj pj ) + A0 p2 = h i i = h(σi σj Ei pj ) + A0 p2 = i¯ i ijk σk Ei pj + i¯ E · p + A0 p2 = −¯ σ · E × p + i¯ E · p + A0 p2 ¯ h h h h
Plugging this back into the equation. Note that our units now put a 4π in the denominator here.
which turns out to be the KleinGordon equation. The Dirac equation naturally incorporates relativistic corrections. They are also quite important to understand. We will ﬁnd that each component of the Dirac spinor represents a state of a free particle at rest that we can interpret fairly easily. When the Dirac equation is used to make a quantum ﬁeld theory of electrons and photons. and gives an additional correction for s states that is found to be correct experimentally. Quantum ElectroDynamics.500 This was an important test of the Dirac equation and it passed with ﬂying colors.
35. we can calculate eﬀects to very high order and compare the calculations with experiment. the simplest solutions of the Dirac equation are those for a free o particle. the interaction with electron spin. We will do this by making a second order diﬀerential equation.
. ∂ mc + ψ ∂xμ h ¯ ∂ ∂ mc + γν γμ ψ ∂xν ∂xμ h ¯ ∂ ∂ ∂ mc ψ γμ ψ + γν γν ∂xν ∂xμ ∂xν ¯ h mc ∂ ∂ ∂ γν γμ ψ+ ψ γν ∂xν ∂xμ h ¯ ∂xν ∂ ∂ mc 2 γν γμ ψ− ψ ∂xν ∂xμ h ¯ ∂ ∂ mc 2 ψ− ψ γμ γν ∂xμ ∂xν h ¯ ∂ ∂ mc 2 ψ−2 ψ (γν γμ + γμ γν ) ∂xμ ∂xν h ¯ ∂ ∂ mc 2 2δνμ ψ−2 ψ ∂xμ ∂xν h ¯ mc 2 ∂ ∂ ψ−2 ψ 2 ∂xμ ∂xμ h ¯ γμ The free electron solutions all satisfy the wave equation. ﬁnding good agreement. Each component satisﬁes the wave (KleinGordon) equation and a solution can be written as a constant spinor times the usual exponential representing a wave.6
Solution of Dirac Equation for a Free Particle
As with the Schr¨dinger equation. We can show that a free particle solution can be written as a constant spinor times the usual free particle exponential. this is an equation for each component of the Dirac spinor ψ. =0 =0 =0 =0 =0 =0 =0 =0 =0
2−
mc h ¯
2
ψ=0
Because we have eliminated the γ matrices from the equation. Start from the Dirac equation and attempt to develop an equation to show that each component has the free particle exponential.
We also have the plus or minus in the relation E = ± p2 c2 + m2 c4 to deal with.
h ψp (x) = up ei(p·x−Et)/¯ 1 We should normalize the state if we want to describe one particle per unit volume: ψ † ψ = V . The Dirac equation can now be used. we get a relation between the momentum and the energy. We haven’t learned much about what each component represents yet. h∂
There is no coupling between the diﬀerent components in this equation.6. This is just the p = 0 case of the the solution above so the energy equation gives E = ±mc2 .501
h ψp = up ei(p·x−Et)/¯
Plugging this into the equation. Again.1
Dirac Particle at Rest
To study this further. the solution can be written as a constant spinor. lets take the simple case of the free particle at rest. which may depend on momentum up .
35. −p2 E2 mc 2 + 2 − =0 2 2 h ¯ h ¯ h ¯ c −p2 c2 + E 2 − m2 c4 = 0 E 2 = p 2 c2 + m 2 c4 E=± p 2 c2 + m 2 c4
Note that the momentum operator is clearly still
h ¯ i∇
and the energy operator is still i¯ ∂t . but. The solutions for a free particle at rest will tell us more about what the diﬀerent components mean. γ4 ψ0 = +ψ0
. ∂ mc + ψ=0 ∂xμ h ¯ mc ∂ h + ψ0 e−iEt/¯ = 0 γ4 ∂(ict) h ¯ mc −E γ4 ψ0 = − ψ0 h ¯c h ¯ ±mc2 mc γ4 ψ0 = ψ0 h ¯c h ¯ γ4 ψ0 = ±ψ0 γμ
This is a very simple equation. we will see that (unlike the equation diﬀerentiated again) the Dirac equation will give us relations between the components of the constant spinor. putting conditions on the spinor ψ0 . times the exponential. Lets take the case of positive energy ﬁrst.
) Deﬁne a 4 by 4 matrix which gives the z component of the spin. For the “negative energy solutions” we have. what we have called ψA . can be used as the two component spinor in the Schr¨dinger equation (with a normalization factor). Lets identify the ﬁrst o component as spin up along the z axis and the second as spin down. Recall that we have demonstrated that the ﬁrst two components of ψ are large compared to the other two for a nonrelativistic electron solution and that the ﬁrst two components. for a free particle at rest. ψA . Σz = = = = = 1 (γ1 γ2 − γ2 γ1 ) 2i 1 0 −iσx iσx 0 2i 1 0 σx σy 0 σx σy 2i 1 2i σz 0
0 iσy −
−iσy 0 σy σx 0
− 0 σy σx
0 iσy
−iσy 0
0 iσx
−iσx 0
0 [σx .502 ⎛ 1 ⎜0 ⎝ 0 0 ⎞ ⎞ ⎞⎛ ⎛ 0 0 0 A1 A1 1 0 0 ⎟ ⎜ A2 ⎟ ⎜ A2 ⎟ ⎠ = +⎝ ⎠ ⎠⎝ 0 −1 0 B1 B1 B2 B2 0 0 −1 ⎞ ⎞ ⎛ ⎛ A1 A1 ⎜ A2 ⎟ ⎜ A2 ⎟ ⎠ = +⎝ ⎠ ⎝ −B1 B1 −B2 B2 B1 = B2 = 0 ⎛ ⎞ A1 ⎜A ⎟ ψ0 = ⎝ 2 ⎠ 0 0
We see that the positive energy solutions. ⎛ 1 ⎜0 ⎝ 0 0 ⎞ ⎛ ⎞ ⎞⎛ A1 0 0 0 A1 1 0 0 ⎟ ⎜ A2 ⎟ ⎜ A2 ⎟ ⎠ = −⎝ ⎠ ⎠⎝ B1 B1 0 −1 0 B2 B2 0 0 −1 A1 = A2 = 0 ⎞ ⎛ 0 ⎜ 0 ⎟ ψ0 = ⎝ ⎠ B1 B2
We can describe two spin states for the “negative energy solutions”. σy ] 0 σz
. lets assume that the two components can be used to designate the spin up and spin down states according to some quantization axis. We are free to choose each component of that spinor independently. (We do still have a choice of quantization axis. σy ] 0 [σx . For now. are described by the upper two component spinor.
35.2
Dirac Plane Wave Solution
We now have simple solutions for spin up and spin down for both positive energy and “negative energy” particles at rest. γμ mc ∂ + ∂xμ h ¯ ψ=0
h ψp (x) = up ei(pρ xρ )/¯ mc ipμ + γμ ψ=0 h ¯ h ¯
γi =
0 iσi 1 0
−iσi 0 0 −1 0
E c h + mc up ei(pρ xρ )/¯ = 0
γ4 = p·σ 0
0 −p · σ
+
−E c 0
−E + mc2 −cp · σ 0 1 1 0 ⎛ −E + mc2 0 ⎜ ⎝ −pz c −(px + ipy )c σx = 0 −i i 0 0 pz c −E + mc2 (px + ipy )c −(px − ipy )c E + mc2 pz c 0 σy =
cp · σ E + mc2 σz =
up = 0 1 0 0 −1 ⎞
(px − ipy )c −pz c ⎟ ⎠ up = 0 0 E + mc2
.−¯ /2 = √ h V 1 ψ (4) = ψE=−mc2 . So the four normalized solutions for a Dirac particle at rest are. The ﬁrst and second are positive energy solutions while the third and fourth are “negative energy solutions”. The solutions for nonzero momentum are not as simple.
1 ψ (1) = ψE=+mc2 . We could also deﬁne 4 by 4 matrices for the x and y components of spin by using cyclic permutations of the above.6. the third component is the one with spin up along the z direction for the “negative energy solutions”.503 With this matrix deﬁning the spin. which we still need to understand.−¯ /2 = √ h V
⎛ ⎞ 0 ⎜ 1 ⎟ −imc2 t/¯ h ⎝ ⎠e 0 ⎛0⎞ 0 ⎜ 0 ⎟ +imc2 t/¯ h ⎝ ⎠e 0 1
The ﬁrst and third have spin up while the second and fourth have spin down.+¯ /2 = √ h V
⎛ ⎞ 1 ⎜ 0 ⎟ −imc2 t/¯ h ⎝ ⎠e 0 ⎛0⎞ 0 ⎜ 0 ⎟ +imc2 t/¯ h ⎝ ⎠e 1 0
1 ψ (2) = ψE=+mc2 .+¯ /2 = √ h V 1 ψ (3) = ψE=−mc2 .
pz c B1 = E + mc2 (px + ipy )c B2 = E + mc2 ⎛ ⎞ p2 c2 2 −E + mc + E+mc2 ⎜ pz (px +ipy )c2 −pz (px +ipy )c2 ⎟ ⎜ ⎟=0 E+mc2 ⎝ ⎠ 0 0 ⎛ −E 2 +(mc2 )2 +p2 c2 ⎞ ⎜ ⎜ ⎝
E+mc2
0 0 0
⎟ ⎟=0 ⎠
This will be a solution as long as E 2 = p2 c2 + (mc2 )2 . ⎛ ⎞ 1 ⎜ ⎟ 0 (1) h ψp = N ⎜ pz c ⎟ ei(p·x−Et)/¯ ⎝ E+mc2 ⎠
(px +ipy )c E+mc2
We again see that for a nonrelativistic electron. We can therefore identify this as that same solution boosted to have momentum p. Lets start with one that gives a spin up electron in the ﬁrst two components and plug it into the Dirac equation to see what the third and fourth components can be for a good solution. The fact that the last two components are nonzero does not mean it contains “negative energy” solutions. ⎞ ⎛ 1 ⎟ ⎜ 0 up = N ⎜ pz c ⎟ ⎝ E+mc2 ⎠
(px +ipy )c E+mc2
up=0
⎛ ⎞ 1 ⎜0⎟ =N⎝ ⎠ 0 0
This reduces to the spin up positive energy solution for a particle at rest as the momentum goes to zero. The full solution is. ⎞⎛ ⎞ ⎛ 1 −E + mc2 0 pz c (px − ipy )c 2 (px + ipy )c −pz c ⎟ ⎜ 0 ⎟ 0 −E + mc ⎜ ⎠⎝ ⎠=0 ⎝ −pz c B1 −(px − ipy )c E + mc2 0 2 −(px + ipy )c pz c 0 E + mc B2 ⎛ ⎞ 2 −E + mc + B1 pz c + B2 (px − ipy )c B1 (px + ipy )c − B2 pz c ⎜ ⎟ ⎝ ⎠=0 −pz c + B1 (E + mc2 ) −(px + ipy )c + B2 (E + mc2 ) Use the third and fourth components to solve for the coeﬃcients and plug them in for a check of the result. not a surprising condition. This solution is that for a positive energy electron.
. Adding a normalization factor. the last two components are small compared to the ﬁrst.504 We should ﬁnd four solutions. the solution is.
we get the next solution following the same procedure. ⎛ −E + mc2 0 ⎜ ⎝ −pz c −(px + ipy )c 0 −E + mc2 −(px − ipy )c pz c ⎛ ⎞⎛ ⎞ pz c (px − ipy )c 0 (px + ipy )c −pz c ⎟ ⎜ 1 ⎟ ⎠⎝ ⎠=0 E + mc2 0 B1 2 0 E + mc B2 ⎞ B1 pz c + B2 (px − ipy )c ⎜ −E + mc2 + B1 (px + ipy )c − B2 pz c ⎟ ⎝ ⎠=0 −(px − ipy )c + B1 (E + mc2 ) pz c + B2 (E + mc2 ) (px − ipy )c B1 = E + mc2 −pz c B2 = E + mc2 ⎛ pz (px −ipy )c2 −pz (px −ipy )c2 ⎞ ⎜ ⎜ ⎝
E+mc2
−E + mc2 + 0 0 ⎛ ⎜ ⎝
p2 c2 E+mc2
⎟ ⎟=0 ⎠ ⎞ ⎟ ⎠=0
−E 2 +(mc2 )2 +p2 c2 E+mc2
0
0 0
E 2 = p2 c2 + (mc2 )2 ⎛ ⎞ 0 ⎜ ⎟ 1 up = N ⎜ (px −ipy )c ⎟ ⎝ E+mc2 ⎠ ⎛ ⎞ 0 ⎜1⎟ =N⎝ ⎠ 0 0
−pz c E+mc2
up=0
This reduces to the spin down positive energy solution for a particle at rest as the momentum goes to zero. ⎛ ⎜ ⎟ (2) h ψp = N ⎜ (px −ipy )c ⎟ ei(p·x−Et)/¯ ⎝ ⎠
E+mc2 −pz c E+mc2
0 1
⎞
Now we take a look at the “negative energy” spin up solution in the same way. ⎛ −E + mc2 0 ⎜ ⎝ −pz c −(px + ipy )c 0 −E + mc2 −(px − ipy )c pz c pz c (px + ipy )c E + mc2 0 ⎞⎛ ⎞ (px − ipy )c A1 −pz c ⎟ ⎜ A2 ⎟ ⎠⎝ ⎠=0 0 1 0 E + mc2
. The full solution is.505 If we make the upper two components those of a spin down electron.
⎛ −E + mc2 0 ⎜ ⎝ −pz c −(px + ipy )c 0 −E + mc2 −(px − ipy )c pz c pz c (px + ipy )c E + mc2 0
(4) ψp
⎞⎛ ⎞ (px − ipy )c A1 −pz c ⎟ ⎜ A2 ⎟ ⎠⎝ ⎠=0 0 0 2 1 E + mc ⎛ −(px −ipy )c ⎞
−E+mc2 pz c −E+mc2
⎜ =N⎜ ⎝
0 1
⎟ i(p·x−Et)/¯ h ⎟e ⎠
with E being a negative number. Finally. spin down solution follows the same pattern. The full solution is ⎛ −pz c ⎞
(3) ψp
⎜ −(px +ipy )c ⎟ h = N ⎜ −E+mc2 ⎟ ei(p·x−Et)/¯ ⎝ ⎠ 1 0
−E+mc2
with E being a negative number. We will eventually understand the “negative energy” solutions in terms of antielectrons otherwise known as positrons. the “negative energy”.
.506 ⎛ ⎞ A1 (−E + mc2 ) + pz c 2 A2 (−E + mc ) + (px + ipy )c ⎜ ⎟ ⎝ ⎠=0 −A1 pz c − A2 (px − ipy )c + (E + mc2 ) −A1 (px + ipy )c + A2 pz c −pz c A1 = −E + mc2 −(px + ipy )c A2 = −E + mc2 ⎛ ⎞ 0 ⎜ ⎟ 0 ⎜ ⎟=0 p2 c2 2 ⎝ ⎠ 2 + (E + mc ) −E+mc
−pz c − −E+mc2 (px + ipy )c + ⎛ −(px +ipy )c −E+mc2 pz c
⎜ ⎝ −E 2 +(mc
2
)2 +p2 c2 −E+mc2
0 02 0
⎞ ⎟ ⎠=0
E = p2 c2 + (mc2 )2 ⎛ −pz c ⎞ ⎜ −(px +ipy )c ⎟ up = N ⎜ −E+mc2 ⎟ ⎝ ⎠ 1 ⎛ ⎞ 0 ⎜0⎟ =N⎝ ⎠ 1 0 0
−E+mc2
up=0
This reduces to the spin up “negative energy” solution for a particle at rest as the momentum goes to zero.
For solutions 1 and 2. mc2 (r) i(p·x−Et)/¯ (r) h u e ψp ≡ EV p ⎛ up =
(1) (r)
E + mc2 ⎜ ⎜ 2mc2 ⎝ ⎛
1 0
⎞ ⎟ ⎟ ⎠ up =
(2)
⎛
(3) up
=
−E + mc2 ⎜ ⎜ 2mc2 ⎝
pz c E+mc2 (px +ipy )c E+mc2 ⎞ −pz c −E+mc2 −(px +ipy )c ⎟ −E+mc2 ⎟
⎟ E + mc2 ⎜ ⎜ (px −ipy )c ⎟ 2mc2 ⎝ E+mc2 ⎠ ⎛ −(px −ipy )c ⎞
−pz c E+mc2 −E+mc2 pz c −E+mc2
0 1
⎞
1 0
⎠
(4) up
=
−E + mc2 ⎜ ⎜ 2mc2 ⎝
0 1
⎟ ⎟ ⎠
. E is a positive number. ⎞ ⎞ ⎛ ⎛ 1 0 ⎟ ⎟ 0 1 E + mc2 ⎜ E + mc2 ⎜ (1) (2) h h ⎜ pz c ⎟ ei(p·x−Et)/¯ ⎜ (px −ipy )c ⎟ ei(p·x−Et)/¯ ψp = ψp = ⎝ E+mc2 ⎠ ⎝ E+mc2 ⎠ 2EV 2EV ⎛
(3) ψp (px +ipy )c E+mc2 ⎞ −pz c −E+mc2 −(px +ipy )c ⎟ h −E+mc2 ⎟ ei(p·x−Et)/¯
⎛ −(px −ipy )c ⎞
(4) ψp
−pz c E+mc2
=
E + mc2 ⎜ ⎜ 2EV ⎝
1 0
⎠
=
E + mc2 ⎜ ⎜ 2EV ⎝
−E+mc2 pz c −E+mc2
0 1
⎟ i(p·x−Et)/¯ h ⎟e ⎠
The spinors are orthogonal for states with the same momentum and the free particle waves are orthogonal for diﬀerent momenta. Sakurai picks a normalization of the spinor so that u† u transforms like the fourth component of a vector. ψ†ψ = p 2 c2 (E + mc2 )2 E 2 + m2 c4 + 2Emc2 + p2 c2 (E + mc2 )2 2E 2 + 2Emc2 N2 (E + mc2 )2 2E N2 (E + mc2 ) N2 1 + N= = = = = 1 V 1 V 1 V 1 V 1 V
N2
E + mc2 2EV
We have the four solutions with for a free particle with momentum p. For solutions 3 and 4. Note that the orthogonality condition is the same as for nonrelativistic spinors (r)† (r ) ψp ψp = δrr δ(p − p ) It is useful to write the plane wave states as a spinor up times an exponential.507 We will normalize the states so that there is one particle per unit volume. We will follow the same convention. E is negative.
the ﬁrst and third components must be zero. we can compute the conserved probability current.508 E δrr mc2
up
(r)†
up
(r )
=
Are the free particle states still eigenstates of Σz =
σz 0 as were the states of a particle at rest? 0 σz In general. To have an eigenvalue of +1. mixes up the spin states. If the particle’s momentum is in the z direction. These are called helicity eigenstates. While it is possible to make deﬁnite momentum solutions which are eigenstates of helicity.
(1) (3)
(1)
⎛ ψp = ⎜ N⎜ ⎝
1 0
pz c E+mc2 (px +ipy )c E+mc2
⎞ ⎟ i(p·x−Et)/¯ h ⎟e ⎠
. the spin eigenstates are preserved. and a “negative energy” plane wave. if we boost along the quantization axis. a spinor must have zero second and fourth components and to have an eigenvalue of 1. So boosting our Dirac particle to a frame in which it is moving. To further understand these solutions.
There is one case for which these are still spin eigenstates. ψp . then we have just the spinors we need to be eigenstates of Σz . Helicity is the spin component along the direction of the particle. they are not. First. B1 B2 ¯ jμ = icψγμ ψ jμ = icψ † γ4 γμ ψ ⎛ ⎞ 1 0 0 0 0 ⎟ ⎜0 1 0 γ4 = ⎝ ⎠ 0 0 −1 0 0 0 0 −1 ⎛ ⎞ A1 ⎜A ⎟ ∗ ∗ jμ = ic ( A∗ A∗ −B1 −B2 ) γμ ⎝ 2 ⎠ 1 2 B1 B2 ⎛ γ1 = ⎛ ⎞ 0 0 −i 0 0 −i 0 ⎟ ⎜ 0 γ2 = ⎝ ⎠ i 0 0 0 0 0 0 −1 ∗ ∗ ⎞ A∗ B2 + A1 B2 + A∗ B1 + A2 B1 1 2 ∗ ∗ ∗ ∗ ⎜ −i[A1 B2 − A1 B2 − A2 B1 + A2 B1 ] ⎟ c⎝ ∗ ∗ ∗ ∗ ⎠ A1 B1 + A1 B1 − A2 B2 − A2 B2 ∗ ∗ i[A∗ A1 + A∗ A2 + B1 B1 + B2 B2 ] 1 2 0 ⎜0 ⎝ 0 i ⎛ 0 0 1 0 0 1 0 0 ⎞ −1 0 ⎟ ⎠ 0 0 0 ⎜0 γ3 = ⎝ i 0 ⎛ ⎞ 0 −i 0 0 0 i⎟ ⎠ 0 0 0 −i 0 0
jμ
=
Now compute it speciﬁcally for a positive energy plane wave. compute it in general for a Dirac spinor ⎞ ⎛ A1 ⎜A ⎟ ψ = ⎝ 2 ⎠. it is not possible to make deﬁnite momentum states which are eigenstates of spin along some other direction (except in the trivial case of p = 0 as we have shown). ψp . That is.
For solutions 3 and 4.3
Alternate Labeling of the Plane Wave Solutions
Start from the four plane wave solutions: 1 and 2 with positive energy and 3 and 4 with negative. −i[−A∗ + A2 ]. For solutions 3 and 4. [A∗ + A1 ].
dω ˆ dE k= p=± ˆ dk dp
. Perhaps the momentum and energy operators we developed in NR quantum mechanics are not the whole story. pz c. i[−E + mc2 + −E + mc2 −E + mc2 2c −N 2 (px c. −2py c. py c.6. we want waves that propagate in the right direction. i[A∗ A1 + A∗ A2 + 1]) 2 2 1 1 2 c p 2 c2 ] −2pxc. i[1 + B1 B1 + B2 B2 ])
= = =
c p 2 c2 ] [2px c]. [2py c]. There are four solutions for each choice of momentum p. ⎞ ⎞ ⎛ ⎛ 1 0 ⎟ ⎟ 0 1 E + mc2 ⎜ E + mc2 ⎜ (1) (2) h h ⎜ pz c ⎟ ei(p·x−Et)/¯ ⎜ (px −ipy )c ⎟ ei(p·x−Et)/¯ ψp = ψp = 2EV ⎝ E+mc2 ⎠ 2EV ⎝ E+mc2 ⎠ ⎛ ψp =
(3) (px +ipy )c E+mc2 ⎞ −pz c −E+mc2 −(px +ipy )c ⎟ h −E+mc2 ⎟ ei(p·x−Et)/¯
⎛ ψp =
(4)
E + mc2 ⎜ ⎜ 2EV ⎝
1 0
⎠
E + mc2 ⎜ ⎜ 2EV ⎝
−pz c E+mc2 −(px −ipy )c −E+mc2 pz c −E+mc2
⎞ ⎟ i(p·x−Et)/¯ h ⎟e ⎠
0 1
Concentrate on the exponential which determines the wave property. iE) −E + mc2 N2
Since E is negative for the “negative energy” solution.509
(1) jμ (1) jμ (1) jμ ∗ ∗ ∗ ∗ ∗ N 2 c ([B2 + B2 . −2pz c. vphase = vgroup = ωˆ E k= p=± ˆ k p p 2 c2 + m 2 c4 p ˆ p pc2
p ˆ p 2 c2 + m 2 c4 Clearly. [B1 + B1 ].
35. iE) E + mc2 N2 ⎛
−pz c −E+mc2 −(px +ipy )c −E+mc2
⎞ ⎟ i(p·x−Et)/¯ h ⎟e ⎠
ψp
(3)
=
⎜ N⎜ ⎝
1 0
(3) jμ (3) jμ (3) jμ
= = =
N 2 c ([A∗ + A2 ]. py c. the probability density is positive but the probability ﬂux is in the opposite direction of the momentum. [2pz c]. −i[B2 − B2 ]. pz c. both the phase and group velocity are in the opposite direction to the momentum. i[E + mc2 + 2 E + mc E + mc2 2c N2 (px c. pick the solution for −p to classify with solutions 1 and 2 with momentum p write everything in terms of the positive square root E = p2 c2 + m2 c4 . indicating we have a problem that was not seen in nonrelativistic quantum mechanics.
The negative exponent electron solutions can be recast as conventional exponent positron solutions. he hoped to have an equation that behaved like the Schr¨dinger equation. The Dirac equation also has “negative o energy” solutions. We have no good reason to associate the e−i(pμ xμ ) solution with negative energy. By developing and equation that was ﬁrst order in the time derivative. For relativistic quantum mechanics.
. In fact we picked the + sign somewhat randomly in the development of NR quantum mechanics. Thus. An electron which is localized in space.) The more localized the state. Lets assume it also has positive energy but happens to have the .sign on the whole exponent. (While we are dealing with free particle solutions. we can turn the negative exponent solution (going backward in time) into the conventional positive exponent solution if we change the charge to +e.) ∂ mc ψ=0 γμ ψ + ∂xμ h ¯ ∂ ie mc ψ=0 + Aμ γμ ψ + ∂xμ h ¯c h ¯
∂ The ∂xμ operating on the exponential produces ±ipμ /¯ . the ﬂux that we have derived is in the opposite direction of the momentum vector for the “negative energy” solutions. the equation remains the same. the greater the “negative energy” content. we can consider that nearly free particles will have a very similar exponential term.510
⎛ ψp =
(1)
E + mc2 ⎜ ⎜ 2EV ⎝ ⎛ E + mc2 ⎜ ⎜ 2EV ⎝
(3) ψp
=
h ⎟ ei(p·x−Et)/¯ pz c ⎠ E+mc2 (px +ipy )c E+mc2⎞ pz c E+mc2 (px +ipy )c ⎟ h E+mc2 ⎟ e−i(p·x−Et)/¯
1 0
⎞ ⎟ ψp =
(2)
⎛
⎟ E + mc2 ⎜ h ⎜ (px −ipy )c ⎟ ei(p·x−Et)/¯ ⎝ E+mc2 ⎠ 2EV
E+mc ⎛ (px −ip2 )c ⎞ y −pz c
0 1
⎞
1 0
⎠
(4) ψp
=
E + mc2 ⎜ ⎜ 2EV ⎝
E+mc2 −pz c E+mc2
0 1
⎟ −i(p·x−Et)/¯ h ⎟e ⎠
We have plane waves of the form
h e±i(pμ xμ )/¯
which is not very surprising. Recall that the momentum has already been inverted (and the spin also will be inverted). will have components of its wave function which are “negative energy”. While the probability is positive. If we change the charge on the electron from h −e to +e and change the sign of the exponent. an equation for a single particle. both solutions are needed.
35. We cannot discount the “negative energy” solutions since the positive energy solutions alone do not form a complete set.7
“Negative Energy” Solutions: Hole Theory
Dirac’s goal had been to ﬁnd a relativistic equation for electrons which was free of the negative probabilities and the “negative energy” states of the KleinGordon equation. Consider the Dirac equation with the EM ﬁeld term included. (The inﬁnite plane wave solutions we have found can be all positive energy.
Dirac postulated a solution to this problem.511 One problem of the “negative energy” states is that an electron in a positive energy (bound or free) state should be able to emit a photon and make a transition to a “negative energy” state. When the Dirac ﬁeld is quantized. As we saw in the nonrelativistic limit. The process of moving an electron to a positive energy state is like pair creation. this must be done near a nucleus (for example)). (Actually to conserve momentum and energy.
.8
Equivalence of a Two Component Theory
The two component theory with ψA (and ψB depending on it) is equivalent to the Dirac theory. We might just relabel p → −p since these solutions go in the opposite direction anyway and change the sign of E so that it is positive. Suppose that all of the “negative energy” states are all ﬁlled and the Pauli exclusion principle keeps positive energy electrons from making transitions to them. The exponential would be then change to
h h ei(p·x−Et)/¯ → e−i(p·x−Et)/¯
with e positive and p in the direction of probability ﬂux. The process could continue giving oﬀ an inﬁnite amount of energy. The discovery of the positron gave a great deal of support to the hole theory. A decision must be made when we determine how many independent ﬁelds there are.
35. What about all that charge and negative energy? Why is there an asymmetry in the vacuum between negative and positive energy when Dirac’s equation is symmetric? (We could also have said that positrons have positive energy and there is an inﬁnite sea of electrons in negative energy states. It has positive energy relative to the vacuum.) This is probably not the right answer but it has many elements of truth in it. it produces both an electron and a hole which we interpret as a positron. The Dirac theory has many advantages in terms of notation and ease of forming Lorentz covariant objects. It also gives the right result for some simple calculations. we will no longer need the inﬁnite “negative energy” sea. The normalization correction would be very large for the “negative energy” states if we continued to use ψA . It has a second order equation and separate negative and positive energy solutions. the normalization condition is a bit unnatural in the two component theory. A hole would be left behind in the usual vacuum which has a positive charge relative to the vacuum in which all the “negative energy” states are ﬁlled. Another way to look at the “negative energy” solution is as a positive energy solution moving backward in time. but electrons and positrons will behave as if it were there. It has momentum and spin in the opposite direction of the empty “negative energy” state. The particle would move in the opposite direction of its momentum. The positive energies must all be bigger than mc2 and the negative energies must all be less than −mc2 . This hole has all the properties of a positron. The minimum photon energy that could cause this would be 2mc2 . There is an energy gap of 2mc2 . we only need to specify the wave function and whether it is negative or positive energy to do the time development. The idea of an inﬁnite sea of “negative energy” electrons is a strange one. This makes the same change of the sign in the exponential. It would be possible for a “negative energy” electron to absorb a photon and make a transition to a positive energy state. Even though it is a second order diﬀerential equation. It would also behave as if it had the opposite charge.
For a rotation about the j axis. We wish to ﬁnd the transformation matrices for the equations. can be covariant. The four components if the Dirac spinor do not represent x. Remember that spinors transform under rotations in a way quite diﬀerent from normal vectors. with its constant γ matrices. aμν (a)−1 νλ S
−1
= = = =
δμλ δμλ γν aλν γν aλν
aμν aλν γμ Saμν aλν S −1 γλ S
. ψ ψ = = Srot (θ)ψ Sboost (β)ψ
We will work with the Dirac equation and its transformation. R(θ) = cos θ θ + iσj sin 2 2
We can think of rotations and boosts as the two basic symmetry transformations that we can make in 4 dimensions. (Remember that aμν works in an entirely diﬀerent space than do γμ and S. the result was. ﬁnding that they are quite diﬀerent than rotation matrices for 2 vectors.9
Relativistic Covariance
It is important to show that the Dirac equation. We know how the Lorentz vectors transform so we can derive a requirement on the spinor transformation. and t. Multiply by the inverse Lorentz transformation. This will come down to ﬁnding the right transformation of the Dirac spinor ψ. We derived the rotation matrices for spin 1 states. z. y. We have already solved a similar problem.) ∂ mc ψ(x) = ψ(x) + ∂xμ h ¯ mc ∂ γμ ψ (x ) + ψ (x ) = ∂xμ h ¯ γμ ψ (x ) ∂ ∂xμ ∂ mc Sψ γμ aμν Sψ + ∂xν h ¯ mc ∂ S −1 γμ aμν Sψ Sψ + ∂xν h ¯ mc −1 ∂ S Sψ S −1 γμ Saμν ψ+ ∂xν h ¯ ∂ mc ψ S −1 γμ Saμν ψ+ ∂xν h ¯ = = = = = = 0 0 Sψ(x) ∂ aμν ∂xν 0 0 0 0
The transformed equation will be the same as the Dirac equation if S −1 γμ Saμν = γν .512
35.
We deﬁne tanh χ = β. Rotations and boosts are symmetry transformations of the coordinates in 4 dimensions. tanh χ cosh χ sinh χ = = = eχ − e−χ =β eχ + e−χ eχ + e−χ 2 eχ − e−χ 2 e−χ + eχ ei(iχ) + e−i(iχ) = = cosh χ 2 2 ei(iχ) − e−i(iχ) e−χ − eχ eχ − e−χ = =i = i sinh χ 2i 2i 2 1 1 1 = = = 2 2 (1 + tanh χ)(1 − tanh χ) 1−β 1 − tanh χ tanh χ cosh χ = sinh χ ⎛ a(boost) μν x1 x x4 = = = = ⎞ cosh χ 0 0 i sinh χ 0 1 0 0 ⎟ ⎜ ⎝ ⎠ 0 0 1 0 −i sinh χ 0 0 cosh χ x1 cosh χ + ix4 sinh χ γx + βγi(ict) x4 cosh χ − ix1 sinh χ
cos(iχ) = sin(iχ) = γ βγ = =
1
2eχ 2e−χ eχ +e−χ eχ +e−χ
=
eχ + e−χ = cosh χ 2
We verify that a boost along the i direction is like a rotation in the i4 plane through an angle iχ. For example a boost with velocity β in the x direction is like a rotation in the 14 plane by an angle iχ.513
S −1 γμ S = γν aμν
This is the requirement on S for covariance of the Dirac equation. as examples. Let us review the Lorentz transformation for boosts in terms of hyperbolic functions.
. Consider the cases of rotations about the z axis and boosts along the x direction. ⎛ ⎞ cos θ sin θ 0 0 ⎜ − sin θ cos θ 0 0 ⎟ a(rot) = ⎝ ⎠ μν 0 0 1 0 0 0 0 1 ⎛ ⎞ ⎛ ⎞ γ 0 0 iβγ cosh χ 0 0 i sinh χ 1 0 0 ⎟ ⎜ 0 1 0 0 ⎟ ⎜ 0 a(boost) = ⎝ ⎠=⎝ ⎠ μν 0 0 1 0 0 0 1 0 −iβγ 0 0 γ −i sinh χ 0 0 cosh χ The boost is just another rotation in Minkowski space through and angle iχ = i tanh−1 β.
Recalling that the 4 component equivalent of σz is Σz = [γ12i 2 ] = γ1iγ2 . Srot Sboost = = θ θ + γ1 γ2 sin 2 2 χ χ cosh + iγ1 γ4 sinh 2 2 cos
Note that this is essentially the transformation that we derived for rotations of spin onehalf states extended to 4 components. we will show that these matrices are (for a rotation in the xy plane and a boost in the x direction). χ χ χ χ χ χ γ1 cosh2 + iγ1 γ1 γ4 cosh sinh − iγ1 γ4 γ1 cosh sinh + γ1 γ4 γ1 γ1 γ4 sinh2 = a1ν γν 2 2 2 2 2 2 χ χ χ χ χ χ γ1 cosh2 + iγ4 cosh sinh + iγ4 cosh sinh + γ1 sinh2 = a1ν γν 2 2 2 2 2 2 χ χ χ χ = a1ν γν γ1 cosh2 + 2iγ4 cosh sinh + γ1 sinh2 2 2 2 2 cosh2
−χ χ −χ 1 χ χ χ 1 + sinh2 = ((e 2 + e 2 )2 + (e 2 − e 2 )2 ) = (eχ + 2 + e−χ + eχ − 2 + e−χ ) 2 2 4 4 1 = (eχ + e−χ ) = 2 −χ χ −χ χ 1 χ χ 1 χ 1 −χ cosh sinh = ((e 2 + e 2 )(e 2 − e 2 )) = (e − e ) = sinh χ 2 2 4 4 2 −χ χ −χ 1 χ χ χ cosh2 − sinh2 = ((e 2 + e 2 )2 − (e 2 − e 2 )2 ) 2 2 4 1 = (eχ + 2 + e−χ − eχ + 2 − e−χ ) = 4 γ1 cosh χ + iγ4 sinh χ = ⎛ ⎞ cosh χ 0 0 i sinh χ 0 1 0 0 ⎟ ⎜ aμν = ⎝ ⎠ 0 0 1 0 −i sinh χ 0 0 cosh χ γ1 cosh χ + iγ4 sinh χ = γ1 cosh χ + iγ4 sinh χ
cosh χ
1 a1ν γν
. γν } = 2δμν . First check γ1 . which tells us that the square of any gamma matrix is one and that commuting a pair of (unequal) matrices changes the sign.514 We need to ﬁnd the transformation matrices S that satisfy the equation S −1 γμ S = γν aμν for the .γ Dirac equation to be covariant. χ χ χ −1 χ + iγ1 γ4 sinh γμ cosh + iγ1 γ4 sinh 2 2 2 2 χ −χ χ −χ + iγ1 γ4 sinh cosh γμ cosh + iγ1 γ4 sinh 2 2 2 2 χ χ χ χ cosh − iγ1 γ4 sinh γμ cosh + iγ1 γ4 sinh 2 2 2 2 χ χ χ χ χ χ χ χ cosh γμ cosh + cosh γμ iγ1 γ4 sinh − iγ1 γ4 sinh γμ cosh − iγ1 γ4 sinh γμ iγ1 γ4 sinh 2 2 2 2 2 2 2 2 χ χ χ χ 2 χ 2 χ + iγμ γ1 γ4 cosh sinh − iγ1 γ4 γμ cosh sinh + γ1 γ4 γμ γ1 γ4 sinh γμ cosh 2 2 2 2 2 2 cosh = aμν γν = aμν γν = aμν γν = aμν γν = aμν γν
The equation we must satisfy can be checked for each γ matrix. The operations with the γ matrices all come from the anticommutator. {γμ . For the case of the boost the angle is now iχ. Lets verify that this choice works for a boost.
aμν = δμν and the requirement is fairly obviously satisﬁed. The pure rotation about the z axis should also be veriﬁed. As a last test. Checking the requirement for μ = 1. θ θ θ θ + γ1 γ2 sin γμ cos + γ1 γ2 sin 2 2 2 2 θ θ θ θ cos − γ1 γ2 sin γμ cos + γ1 γ2 sin 2 2 2 2 θ θ θ θ θ θ γμ cos2 + γμ γ1 γ2 cos sin − γ1 γ2 γμ cos sin − γ1 γ2 γμ γ1 γ2 sin2 2 2 2 2 2 2 cos
−1
= = =
aμν γν aμν γν aμν γν
For μ = 3 or 4. γ1 cos2 θ θ θ θ θ θ + γ1 γ1 γ2 cos sin − γ1 γ2 γ1 cos sin − γ1 γ2 γ1 γ1 γ2 sin2 2 2 2 2 2 2 aμν θ θ θ θ + 2γ2 cos sin − γ1 sin2 2 2 2 2 γ1 cos θ + γ2 sin θ = a1ν γν ⎛ cos θ ⎜ − sin θ = ⎝ 0 0
sin θ cos θ 0 0
0 0 1 0
⎞ 0 0⎟ ⎠ 0 1
γ1 cos2
= cos θγ1 + sin θγ2 = cos θγ1 + sin θγ2
. γ4 cosh2 χ χ χ χ χ χ + iγ4 γ1 γ4 cosh sinh − iγ1 γ4 γ4 cosh sinh + γ1 γ4 γ4 γ1 γ4 sinh2 2 2 2 2 2 2 χ χ χ χ 2 χ 2 χ − iγ1 cosh sinh − iγ1 cosh sinh + γ4 sinh γ4 cosh 2 2 2 2 2 2 χ χ 2 χ 2 χ − 2iγ1 cosh sinh + γ4 sinh γ4 cosh 2 2 2 2 γ4 cosh χ − iγ1 sinh χ = = = = a4ν γν −i sinh χγ1 + cosh χγ4 −i sinh χγ1 + cosh χγ4 −i sinh χγ1 + cosh χγ4
That one also checks.515 That checks for γ1 . try γ2 . try γ4 . Now. we get. γ2 cosh2 χ χ χ χ χ + iγ2 γ1 γ4 cosh sinh − iγ1 γ4 γ2 cosh sinh + γ1 γ4 γ2 γ1 γ4 sinh2 2 2 2 2 2 χ χ χ χ 2 χ + iγ2 γ1 γ4 cosh sinh − iγ2 γ1 γ4 cosh sinh − γ2 sinh2 γ2 cosh 2 2 2 2 2 χ 2 χ 2 γ2 = = = γ2 a2ν γν γ2
The Dirac equation is therefore shown to be invariant under boosts along the xi direction if we transform the Dirac spinor according to ψ = Sboost ψ with the matrix
Sboost = cosh
χ χ + iγi γ4 sinh 2 2
and tanh χ = β.
We can transform the
⎞⎛ ⎞ ⎛ ⎞ 0 −iβγ 0 βγmc 0 0 ⎟⎜ 0 ⎟ ⎜ 0 ⎟ ⎠⎝ ⎠=⎝ ⎠ 1 0 0 0 0 γ imc iγmc
The momentum along the x direction is px = βγmc = mc sinh χ. As an example.+¯ /2 h
The solution we found for a free particle with momentum p was. we might try our solution for a free electron with spin up along the z axis at rest. γμ . We now have two ways to get the free particle state with momentum in the x direction. ⎛ ⎞ ⎛ ⎞ 1 1 1 ⎜ 0 ⎟ −imc2 t/¯ 1 ⎜ 0 ⎟ ipρ xρ /¯ h h = √ ⎝ ⎠e = √ ⎝ ⎠e 0 0 V V 0 0
ψ (1) = ψE=+mc2 . Despite the fact that we are using a vector of constant matrices. We can use our free particle state ⎛ ψ (1) = E+ 2EV mc2 ⎜ ⎝ 1 0 0
px c
2
⎞ ⎟ i(p·x−Et)/¯ h ⎠e ⎞ ⎟ i(p·x−Et)/¯ h ⎟e ⎠
=
⎛ E+mc 1 E + mc2 ⎜ 0 ⎜ 0 2EV ⎝ ⎛
=
⎞ 1 E + mc2 ⎜ 0 ⎟ i(p·x−Et)/¯ h ⎜ ⎟e 2EV ⎝ 0 ⎠
βγ γ+1
βγmc2 γmc2 +mc2
. This allows us to move from one coordinate system to another. the Dirac equation is covariant if we choose the right transformation of the spinors. ⎛ γ 0 1 ⎜ 0 pν = a(boost) pν = ⎝ μν 0 0 iβγ 0
the −x direction with
v c
= β. ⎛ ψp =
(1)
E + mc2 ⎜ ⎜ 2EV ⎝
1 0
pz c E+mc2 (px +ipy )c E+mc2
⎞ ⎟ ip x /¯ ⎟e ρ ρ h ⎠
Imagine we boost the coordinate system along momentum of the electron to the new frame.516 This also proves to be the right transformation of ψ so that the Dirac equation is invariant under rotations about the k axis if we transform the Dirac spinor according to ψ = Srot ψ with the matrix
Srot = cos
θ θ + γi γj sin 2 2
and ijk is a cyclic permutation.
χ χ Sboost = cosh − iγ1 γ4 sinh 2 2 ⎛ ⎞⎛ ⎞ 0 0 0 −i 1 0 0 0 χ χ 0 ⎟ ⎜ 0 0 −i 0 ⎟ ⎜ 0 1 0 = cosh − i ⎝ ⎠⎝ ⎠ sinh 0 i 0 0 0 0 −1 0 2 2 i 0 0 0 0 0 0 −1 ⎛ ⎞ 0 0 0 i χ χ ⎜0 0 i 0⎟ = cosh − i ⎝ ⎠ sinh 0 i 0 0 2 2 i 0 0 0 ⎛ ⎞ 0 0 0 1 χ ⎜0 0 1 0⎟ χ = cosh + ⎝ ⎠ sinh 0 1 0 0 2 2 1 0 0 0 ⎞ ⎛ cosh χ 0 0 sinh χ 2 2 χ χ cosh 2 sinh 2 0 ⎟ ⎜ 0 = ⎝ ⎠ 0 sinh χ cosh χ 0 2 2 χ χ 0 0 cosh 2 sinh 2 ⎛ ψp
(1)
=
=
0 0 cosh χ 2 0 cosh χ sinh χ ⎜ 2 2 ⎝ 0 sinh χ cosh χ 2 2 sinh χ 0 0 2 ⎛ ⎞ cosh χ 2 1 ⎜ 0 ⎟ ipρ xρ /¯ h √ ⎝ ⎠e 0 V sinh χ 2
⎛ ⎞ ⎞ 1 sinh χ 2 0 ⎟ 1 ⎜ 0 ⎟ ipρ xρ /¯ h ⎠ √ ⎝ ⎠e 0 0 V cosh χ 0 2
.
We can also ﬁnd the same state by boosting the at rest solution. deﬁning this as the primed system. Recall that we are boosting in the x direction with −β. implying χ → −χ.517 ⎛ = E + mc2 ⎜ ⎜ 2EV ⎝ ⎛ = E + mc2 ⎜ ⎜ 2EV ⎝ ⎛ = 1 0 0
sinh χ cosh χ+1
⎞ ⎟ i(p·x−Et)/¯ h ⎟e ⎠ ⎞ ⎟ i(p·x−Et)/¯ h ⎟e ⎠
2 sinh 2 cosh χ 2 2 χ +sinh2 χ +cosh2 χ −sinh2 χ cosh 2 2 2 2
1 0 0 χ
E + mc2 ⎜ ⎜ 2EV ⎝ 2 sinh ⎛ E+ 2EV mc2
=
⎞ 1 ⎜ 0 ⎟ i(p·x−Et)/¯ h ⎝ ⎠e 0 tanh χ 2
√1 V
2 cosh 2 cosh2 χ 2
1 0 0 χ
⎞
χ 2
⎟ i(p·x−Et)/¯ h ⎟e ⎠
where the normalization factor is now set to be
.
∂ mc ψ(x) = ψ(x) + ∂xμ h ¯ ∂ mc ψ (x ) = γμ ψ (x ) + ∂xμ h ¯ γμ ψ (x ) = ∂ = ∂xj ∂ ∂x4 −γj
−1 SP
0 0 SP ψ(x) ∂ − ∂xj ∂ ∂x4 0 0
= = =
∂ ∂ mc SP ψ + γ4 SP ψ + ∂xj ∂x4 h ¯ mc ∂ ∂ ψ + γ4 −γj SP ψ + ∂xj ∂x4 h ¯
.518 ⎞ 1 χ ⎜ 0 ⎟ ipρ xρ /¯ 1 h √ cosh ⎝ ⎠e 0 2 V tanh χ 2 ⎛
eχ +e−χ 2
−χ 2
=
1 + cosh χ 2 cosh χ 2
= =
1+
2
eχ + 2 + e−χ = = 4
e2 + e 2
χ
2
= cosh2
χ 2
ψp
(1)
=
=
=
1+γ E + mc2 = 2 2mc2 ⎛ ⎞ 1 E + mc2 ⎜ 0 ⎟ ipρ xρ /¯ 1 h √ ⎝ ⎠e 0 2mc2 V tanh χ 2 ⎛ ⎞ 1 E + mc2 ⎜ 0 ⎟ ipρ xρ /¯ 1 h √ ⎝ ⎠e 0 2mc2 γV tanh χ 2 ⎛ ⎞ 1 E + mc2 ⎜ 0 ⎟ ipρ xρ /¯ h ⎝ ⎠e 0 2EV tanh χ 2 1 + cosh χ = 2
V γ
In the last step the simple Lorentz contraction was used to set V = the plane wave solution including the normalization. This boosted state matches
35.
.10
Parity
It is useful to understand the eﬀect of a parity inversion on a Dirac spinor. Again work with the Dirac equation and its parity inverted form in which xj → −xj and x4 remains unchanged (the same for the vector potential).
) Therefore.11
Bilinear Covariants
We have seen that the constant γ matrices can be used to make a conserved vector current ¯ jμ = icψγμ ψ that transforms correctly under Lorentz transformations. With 4 by 4 matrices. ¯ ψ = (Sψ)† γ4 = ψ † S † γ4 Looking at the two transformations.
⎛
35. but there is no point to it. the third and fourth components of the spinor change sign while the 0 0 −1 0 0 0 0 −1 ﬁrst two don’t. it works ﬁne. The vector above represents 4 of those. The Dirac spinor is transformed by the matrix S. ψ = Sψ ¯ This implies that ψ = ψ † γ4 transforms according to the equation. we can write the inverse transformation. SP = γ4 (We could multiply it by a phase factor if we want.519 Since γ4 commutes with itself but anticommutes with the γi . under a parity inversion operation
ψ = SP ψ = γ4 ψ
⎞ 1 0 0 0 0 ⎟ ⎜0 1 0 Since γ4 = ⎝ ⎠. Since we could have chosen −γ4 . we should be able to make up to 16 components. θ θ + γi γj sin 2 2 χ χ Sboost = cosh + iγi γ4 sinh 2 2 θ θ −1 Srot = cos − γi γj sin 2 2 χ χ −1 Sboost = cosh − iγi γ4 sinh 2 2 θ θ θ θ † Srot = cos + γj γi sin = cos − γi γj sin 2 2 2 2 χ χ χ χ = cosh − iγ4 γi sinh = cosh + iγi γ4 sinh 2 2 2 2 θ θ † −1 γ4 Srot γ4 = cos − γi γj sin = Srot 2 2 Srot = cos
† Sboost
. all we know is that components 3 and 4 have the opposite parity of components 1 and 2.
To get an axial vector and a pseudoscalar. Similarly. γ5 commutes with S since it commutes with the pair of gamma matrices. γ5 = γ1 γ2 γ3 γ4 which obviously anticommutes with all the gamma matrices. Note that things like γ5 σ12 = iγ1 γ2 γ3 γ4 γ1 γ2 = −iγ3 γ4 is just a constant times another antisymmetric tensor element. γ5 } = 0 For rotations and boosts. It transforms like a Lorentz vector under parity. {γμ . This now brings our total to 16 components of bilinear (in the spinor) covariants. we deﬁne the product of all gamma matrices.
. so its nothing new. Therefore its easy to show that ψγ5 ψ transforms ¯ like a pseudoscalar and ψiγ5 γμ ψ transforms like an axial vector. We now have 1+4+6 components for the scalar. Under the parity transformation ¯ ¯ ¯ ψ γμ ψ = ψS −1 γμ Sψ = ψγ4 γμ γ4 ψ the spacial components of the vector change sign and the fourth component doesn’t. ¯ ¯ ¯ ψ ψ = ψS −1 Sψ = ψψ ¯ Repeating the argument for ψγμ ψ we have ¯ ¯ ¯ ψ γμ ψ = ψS −1 γμ Sψ = aμν ψγν ψ according to our derivation of the transformations S. SP = γ4
† SP = γ4 −1 SP = γ4 † −1 γ4 SP γ4 = γ4 γ4 γ4 = γ4 = SP
¯ From this we can quickly get that ψψ is invariant under Lorentz transformations and hence is a scalar. ¯ ¯ ψσμν ψ ≡ ψiγμ γν ψ forms a rank 2 (antisymmetric) tensor. it anticommutes with SP = γ4 . for μ = ν. vector and rank 2 antisymmetric tensor.520 χ χ −1 − iγi γ4 sinh = Sboost 2 2 γ4 S † γ4 = S −1 ¯ ¯ ψ = (Sψ)† γ4 = ψ † γ4 γ4 S † γ4 = ψ † γ4 S −1 = ψS −1
† γ4 Sboost γ4 = cosh
This also holds for SP . For ¯ a parity inversion.
Σz = γ1 γ2 [γ1 . we need to separate the space and time derivatives. vector. of Components 1 1 4 4 6 16
The γ matrices can be used along with Dirac spinors to make a Lorentz scalar. pseudoscalar.
35. ¯ [H.12
Constants of the Motion for a Free Particle
We know that operators representing constants of the motion commute with the Hamiltonian. For a Hamiltonian formulation. This is the complete set of covariants. which of course could be used together to make up Lagrangians for physical quantities. axial vector and rank 2 tensor. The form of the Dirac equation we have been using does not have a clear Hamiltonian. Lets ﬁnd the Hamiltonian in the Dirac equation. mc ∂ + ψ=0 ∂xμ h ¯ mc ∂ ∂ + + γ4 ψ=0 γj ∂xj ∂ict h ¯ h ¯ ∂ − imc ψ = 0 γj pj − γ4 c ∂t h ¯ ∂ψ (γj pj − imc) ψ = γ4 c ∂t h ¯ ∂ψ (γ4 γj pj − imcγ4 ) ψ = c ∂t icγ4 γj pj + mc2 γ4 ψ = Eψ γμ
H = icγ4 γj pj + mc2 γ4
Its easy to see the pk commutes with the Hamiltonian for a free particle so that momentum will be conserved. This is true essentially because of the covariant form we have been using. Lz ] = icγ4 [γj pj . xpy − ypx ] = hcγ4 (γ1 py − γ2 px ) The components of spin also do not commute with H. The components of orbital angular momentum do not commute with H. All sixteen quantities deﬁned satisfy Γ2 = 1.521 Classiﬁcation Scalar Pseudoscalar Vector Axial Vector Rank 2 antisymmetric tensor Total Covariant Form ¯ ψψ ¯ ψγ5 ψ ¯ ψγμ ψ ¯ ψγ5 γμ ψ ¯ ψσμν ψ no. γ2 ] = 2i i
.
γ4 ] = 2icγ · p 2cγ4 [γ2 px − γ1 py ] −2cγ4 γ × p 2ic(γ · p)(Σ · J − 0 L+ h ¯ Σ 2 h ¯ ) − 2cγ × p · J 2
[H. S · p] = [H. Sz ] = hcγ4 (γ1 py − γ2 px ) + hcγ4 [γ2 px − γ1 py ] = 0 ¯ ¯
The Dirac equation naturally conserves total angular momentum but not conserve the orbital or spin parts of it. Lets compute the commutator recalling that H commutes with the total angular momentum. S] · p = hcγ4 p × γ · p = 0 ¯ From the above commutators [H. [H. We can show that [H. We will need another conserved quantity for the solution to the Hydrogen atom. Σ] · J 2 ic[γ4 γ · p. Lz ] + [H. Jz ] = [H. Sz ]. K] = 0 for 2 K = γ4 Σ · J − h ¯ γ4 . γ4 ](Σ · J − ) + γ4 [H. 2
It is related to the spin component along the total angular momentum direction.522 h ¯ h ¯ h ¯ [H. γ4 ] = [H. [H. the components of total angular momentum do commute with H. K] = p·L = J =
[H. Σz ] = H. Sz ] = [H. H = icγ4 γ · p + mc2 γ4 h ¯ [H. the helicity. γ1 γ2 ] = c pj [γ4 γj γ1 γ2 − γ1 γ2 γ4 γj ] 2 2 2 h ¯ h ¯ ¯ = c pj [γ4 γj γ1 γ2 − γ4 γ1 γ2 γj ] = c pj γ4 [γj γ1 γ2 − γ1 γ2 γj ] = hcγ4 [γ2 px − γ1 py ] 2 2 However. K] =
. K] = [H. Σz ] = c [γ4 γj pj . something akin to the ± in j = ± 1 we used in the NR solution. or spin along the direction of motion does commute. Σ =
[H. Lz ] and [H. K] = (γ · p)(Σ · J) = γi γm γn
mnj
=
h ¯ 2c i(γ · p)(Σ · J) − γ × p · J − i (γ · p) 2 −i γi pi Σj Jj = pi Jj γi γm γn mnj 2 2(δij γ5 γ4 + ijk γk ) −ipi Jj (δij γ5 γ4 + = −iγ5 γ4 p · J − iγ × p · J h ¯ 2c γ5 γ4 p · J + γ × p · J − γ × p · J − i (γ · p) 2
ijk γk )
(γ · p)(Σ · J) = [H.
Σj Lj ] + [Σi .13
The Relativistic Interaction Hamiltonian
The interaction Hamiltonian for the Dirac equation can be deduced in several ways.
. J] = 0 and [Σ · J. γ4 . J] 2 2
This will be zero if [γ4 . J Σ · L. K] = [H. Σj ]Lj 2 2 2 h ¯ = i¯ ijk Σj Lk + 2i ijk Σk Lj = i¯ ( ijk Σj Lk + ijk Σk Lj ) = i¯ ( ijk Σj Lk − h h h 2 = [Li +
ikj Σk Lj )
= i¯ ( h
ijk Σj Lk
−
So for the Hydrogen atom. The simplest for now is to just use the same interaction term that we had for electromagnetism 1 Hint = − jμ Aμ c and identify the probability current multiplied by the charge (e) as the current that couples to the EM ﬁeld. and K form a complete set of mutually commuting operators for a system with four coordinates x. L + h ¯ h ¯ Σ] = [γ4 . H. K] =
It is also useful to show that [K. J] = [Σ · L. Jz . J] − [γ4 . J] = [γ4 Σ · J − h ¯ h ¯ γ4 . [K. we have the interaction Hamiltonian. is linear in A. (EM) ¯ = −eicψγμ ψ jμ Removing the ψ † from the left and ψ from the right and dotting into A. The relativistic interaction has just one term. J] + [3. Lj ] + [Σi . Σ] = 0 2 2
= [Σ · L. J]Σ · J + γ4 [Σ · J. y. Σj Lj ] = Σj [Li . J] + [Σ · Σ. Σj Lj ] = [Li . J] = [Σ · L. Hint = ieγ4 γμ Aμ Note the diﬀerence between this interaction and the one we used in the nonrelativistic case. K] = [H.523 h ¯ 2c γ1 γ2 γ3 γ4 γ4 p · J − i (γ · p) 2 h ¯ 2c γ1 γ2 γ3 p · J − i (γ · p) 2 h ¯ h ¯ 2c γ1 γ2 γ3 p · (L + Σ) − i (γ · p) 2 2 h ¯ 2c γ1 γ2 γ3 p · Σ − i(γ · p) 2 h ¯ 2c (ip · γ − i(γ · p)) = 0 2
[H. J] = 0 so that we have a mutually commuting set of operators to deﬁne our eigenstates. z and electron spin. K] = [H.
35. J 2 . J] = 0. K] = [H. J] h ¯ h ¯ h ¯ Σi . J] = [γ4 . J Σ · J. and is naturally proportional to the coupling e. J = [γ4 .
x] = ic[γ4 γj pj . The operator for velocity in the x direction can be computed from the commutator with the Hamiltonian.
Hint = ieγ4 γk Ak
35. ⎞⎛ ⎞ ⎛ ⎞ 0 0 0 0 0 0 −i 0 0 0 1 1 0 0 ⎟ ⎜ 0 0 −i 0 ⎟ ⎜0 0 1 0⎟ ⎠⎝ ⎠ = c⎝ ⎠ 0 −1 0 0 i 0 0 0 1 0 0 0 0 −1 i 0 0 0 1 0 0 0 ⎛ ⎞⎛ ⎞ ⎛ ⎞ 0 0 0 1 a a ⎜0 0 1 0⎟⎜ b ⎟ ⎜b⎟ c⎝ ⎠ ⎝ ⎠ = λc ⎝ ⎠ 0 1 0 0 c c 1 0 0 0 d d −λ 0 0 1 0 −λ 1 0 =0 0 1 −λ 0 1 0 0 −λ −λ[−λ(λ2 ) − 1(−λ)] − 1[λ(λ) + 1(1)] = 0 λ4 − 2λ2 + 1 = 0 (λ2 − 1)2 = 0 (λ2 − 1) = 0 λ = ±1 vx = ±c
. x] = icγ4 γ1 h ¯ h ¯ vj = icγ4 γj
The velocity operator then is vj = icγ4 γj .1
Phenomena of Dirac States
Velocity Operator and Zitterbewegung
We will work for a while in the Heisenberg representation in which the operators depend on time and we can see some of the general behavior of electrons.524 There is no longer an A2 term with a diﬀerent power of e. We may still assume that A is transverse and that A0 = 0 by choice of gauge. the time dependence of the operators is very simple. x= ˙ i i [H.14. just the usual exponentials. If we work in a state of deﬁnite energy. Its not hard to compute that ⎛ 1 ⎜0 icγ4 γ1 = ic ⎝ 0 0 the velocity eigenvalues (any component) are ±c. This will make our perturbation series also a series in powers of α.14
35.
if we measure the velocity component in any direction. vj }) = h ¯ h ¯ h ¯ i i i 2 (−2Hvj + {vj pj . vj ˙ = = i i i [H. vj (t) ˙ = = i i h (−2Evj + 2c2 pj ) = (−2E(c2 pj /E + (vj (0) − c2 pj /E)e−2iEt/¯ ) + 2c2 pj ) h ¯ h ¯ i i h h ((−2c2 pj + (−2Evj (0) + 2c2 pj )e−2iEt/¯ ) + 2c2 pj ) = (−2Evj (0) + 2c2 pj )e−2iEt/¯ h ¯ h ¯
. diﬀerentiate the above vj (t) = − ˙ 2iE i h h (vj (0) − c2 pj /E)e−2iEt/¯ = (−2Evj (0) + 2c2 pj )e−2iEt/¯ h ¯ h ¯
and compare it to the original derivative. vj }) = (−2Hvj + {vj pj + mc2 γ4 . This seems quite surprising. ⎛ ⎞⎛ ⎞ ⎛ ⎞ 0 0 0 1 a a ⎜0 0 1 0⎟⎜ b ⎟ ⎜b⎟ ⎝ ⎠⎝ ⎠ = λ⎝ ⎠ 0 1 0 0 c c 1 0 0 0 d d ⎛ ⎞ ⎛ ⎞ d a ⎜c⎟ ⎜b⎟ ⎝ ⎠ = ±⎝ ⎠ b c a d ⎞ ⎛ ⎞ ⎛ ⎞ ⎛ ⎞ ⎛ 0 1 0 1 ⎜ 1 ⎟ ⎜0⎟ ⎜1⎟ ⎜ 0 ⎟ u=⎝ u=⎝ ⎠ u=⎝ ⎠ u=⎝ ⎠ ⎠ −1 0 1 0 0 1 0 −1
Thus.) The states of deﬁnite momentum are not eigenstates of velocity for a massive electron. we should either get plus or minus c.525 Thus. while momentum is a constant of the motion for a free electron and behaves as it did in NR Quantum Mechanics. Some further study of this eﬀect is in order to see if there are physical consequences and what is diﬀerent about the Dirac theory in this regard. vj }) = (−2Hvj + 2vj pj ) = (−2Hvj + 2vj pj ) = h ¯ h ¯ h ¯ i (−2Hvj + {vj pj . but we should note that a component of the velocity operator does not commute with momentum. If the electron were massless. velocity operators would commute with momentum. even for a free electron. electrons are actually thought to be massless. the Hamiltonian. or even the other components of the velocity operator. getting an eﬀective mass from interactions with particles present in the vacuum state. velocity behaves very strangely in the Dirac theory. (In more speculative theories of particles. The velocity eigenstates mix positive and “negative energy” states equally. vj }) h ¯ i (−2Hvj + 2c2 pj ) h ¯
This is a diﬀerential equation for the Heisenberg operator vj which we may solve. We attempt to write the derivative in terms of the constants of the motion E and p.
h vj (t) = c2 pj /E + (vj (0) − c2 pj /E)e−2iEt/¯
To check. We may get the diﬀerential equation for the velocity of a free electron by computing the derivative of velocity. vj ] = (−2Hvj + {H.
r up ei(p·x−Et)/¯ EV
The r = 1. There are also very rapid oscillations with some amplitude.14.3
The Expected Velocity and Zitterbewegung
The expected value of the velocity in a plane wave state can be simply calculated. vk = ψ † (icγ4 γk )ψ d3 x 0 ⎜0 = c⎝ 0 1 ⎛ 0 0 1 0 0 1 0 0 ⎞ 1 0⎟ ⎠ 0 0 ⎛ E + mc2 ⎜ ⎜ 2EV ⎝ 1 0
pz c E+mc2 (px +ipy )c E+mc2
⎞ ⎟ ⎟ ⎠
(icγ4 γ1 )up
(1)
.2 E + mc2 Even the Hydrogen bound states have small “negative energy” components. oscillations is at most 2mc2 = mc2 c = (3.3MeV F ) = 1200F/c = 1200×10 0. the (free particle) deﬁnite momentum states form a complete set and we can expand any state in terms of them. we would see the same kind of oscillation in the position if we integrate the above solution for the velocity.2
Expansion of a State in Plane Waves
To show how the negative energy states play a role in Zitterbewegung. Obviously. The amplitude of the oscillations is small for nonrelativistic electrons but grows with momentum (or with localization). pc c3. This operator analysis is not suﬃcient to fully understand the eﬀect of Zitterbewegung but it illustrates the behavior.5MeV (c) 3×1010 This very rapid oscillation is known as Zitterbewegung. 2 terms are positive energy plane waves and the r = 3. the “negative energy” amplitude becomes appreciable. it is convenient to go back to the Schr¨dinger representation and expand an arbitrary state in terms of plane waves.14.
4
ψ(x. 4 states are “negative energy”. Since the energy includes mc2 .
35. The plane waves can be purely either positive or “negative energy”. The cross terms between positive and “negative energy” will give rise to very rapid oscillation of the expected values of both velocity and position. localized states have uncertainty in the momentum and tend to have both positive and “negative energy” components. As with nonrelativistic o quantum mechanics.
h vj (t) = c2 pj /E + (vj (0) − c2 pj /E)e−2iEt/¯
There is a steady motion in the direction of the momentum with the correct magnitude βc. This very rapid motion of the electron means we cannot localize the electron extremely well and gives rise to the Darwin term.
35. however.4 ≈ c1. As the momentum components become relativistic.526 This checks so the solution for the velocity as a function of time is correct. t) =
p r=1
mc2 (r) h cp.14)(197. the period of these −13 2π¯ h π¯ c h = 4 × 10−21 seconds. The diﬀering signs of the energy in the time behavior will give rise to rapid oscillations.
The expected value of the position has similar rapid oscillations. K is a measure of the component of spin along the total angular momentum direction. Sakurai (equation 3. while the total angular momentum operator commutes with the Dirac Hamiltonian.r 2
p k c2 + E
2
4
p r=1 r =3
mc3 ∗ (r )† (r) h c cp.r +cp.
35. Note that we use the fact that u(3. vk = vk =
p r=1
ψ † (icγ4 γk )ψ d3 x
4
cp. neither the orbital angular momentum operator nor the spin operators do commute with H. known as Zitterbewegung.r up iγ4 γk up e−2iEt/¯ E p. Its eﬀect is already included in our calculation as it is the source of the Darwin term. We have shown in the section on conserved quantities that the operator K = γ4 Σ · J − γ4 h ¯ 2
also commutes with the Hamiltonian and with J. We will use K to help solve problems with spherical
.253) computes this. The addition of a spherically symmetric potential does not change these facts.r c∗ up p.15
Solution of the Dirac Equation for Hydrogen
The standard Hydrogen atom problem can be solved exactly using relativistic quantum mechanics. The Zitterbewegung again keeps electrons from being well localized in a deep potential raising the energy of s states.r
(r)†
iγ4 γk up
(r )
h e2iEt/¯
The last sum which contains the cross terms between negative and positive energy represents extremely high frequency oscillations in the expected value of the velocity.527 ⎛ (px +ipy )c ⎞
(1) (icγ4 γ1 )up
=c
E + mc2 ⎜ ⎜ 2EV ⎝
E+mc2 pz c E+mc2
⎛ (px +ipy )c ⎞
(1)† (1) up (icγ4 γ1 )up
0 1
⎟ ⎟ ⎠
E + mc2 c 1 0 = 2EV up
(1)†
pz c E+mc2
(px −ipy )c E+mc2
⎜ ⎜ ⎝
E+mc2 pz c E+mc2
0 1
⎟ ⎟ ⎠
(icγ4 γ1 )up =
(1)
2px c E + mc2 px c c c = 2 2EV E + mc EV p k c2 vk = E
The expected value of a component of the velocity exhibits strange behavior when negative and positive energy states are mixed.4) have “negative energy”. The full solution is a bit long but short compared to the complete eﬀort we made in nonrelativistic QM. We have already seen that (even with no applied ﬁelds).
κ. h We now compare the K 2 and J 2 operators.528 symmetry and ultimately the problem of hydrogen. K2 Σ1 Σ1 Σ1 Σ2 Σi Σj K
2
= = = = = = =
γ4 (Σ · L + h)γ4 (Σ · L + hγ4 ) = (Σ · L + hγ4 )2 ¯ ¯ ¯ Σ · LΣ · L + 2¯ Σ · L + h2 = Σi Li Σj Lj + 2¯ Σ · L + h2 h ¯ h ¯ −γ2 γ3 γ2 γ3 = γ2 γ2 γ3 γ3 = 1 −γ2 γ3 γ3 γ1 = −γ2 γ1 = γ1 γ2 = iΣ3 δij + i
ijk Σk ijk Σk )
Li Lj (δij + i
+ 2¯ Σ · L + h2 h ¯
L2 + iΣ · (L × L) + 2¯ Σ · L + h2 h ¯
(L × L)o = xi pj xm pn
ijk mnl klo
= = =
0+
h ¯ xi δjm pn i
ijk mnl klo
=
h ¯ xi pn i
ijk jnl klo
K2 J2 h κ2 ¯ 2 − h ¯2 4 κ2 κ Kψ
= = = = = =
h ¯ h ¯ − xi pn jik jnl klo = − xi pn (δin δkl − δil δkn ) klo i i h ¯ h ¯ h ¯ − xi pi llo + xi pk kio = − xi pk iko = i¯ Lo h i i i L2 − ¯ Σ · L + 2¯ Σ · L + h2 = L2 + hΣ · L + h2 h h ¯ ¯ ¯ 2 3 h ¯ h L 2 + hΣ · L + ¯ 2 = K 2 − ¯ 4 4 j(j + 1)¯ 2 h j2 + j + 1 4
1 ±(j + ) 2 1 ±(j + )ψ 2
The eigenvalues of K are
. mj . K = = h ¯ h ¯ h ¯ 3¯ h h ¯ = γ4 Σ · L + γ4 Σ · Σ − γ4 = γ4 Σ · L + γ4 − γ4 2 2 2 2 2 σ·L+h ¯ 0 ¯ γ4 Σ · L + hγ4 = 0 −σ · L − ¯ h γ4 Σ · J − γ4
Assume that the eigenvalues of K are given by Kψ = −κ¯ ψ. J 2 . j. We therefore have four mutually commuting operators the eigenvalues of which can completely label the eigenstates: H. The operator K may be written in several ways. Jz . K → nr .
then. We already know the relation = j ± 1 from NR QM. 3 h L2 = J 2 − ¯ σ · L − ¯ h 4 We may solve for the eﬀect of σ · L on the spinor ψ.
. they are eigenstates of L2 but have diﬀerent eigenvalues. So ψA and ψB are eigenstates of L2 but with diﬀerent eigenvalues. solve for the eﬀect of L2 . 1 2 h ¯ ψA ψB
=∓ j+
The diﬀerence between J 2 and L2 is related to σ · L. but are opposite for energy eigenstates.
We may explicitly write out the eigenvalue equation for K for κ = ± j + Kψ = −κ¯ ψ = h σ·L+h ¯ 0 0 −σ · L − ¯ h ψA ψB
1 2
h ¯. We simply check 2 that it is the same here. Note that since ψA and ψB are eigenstates of J 2 and σ · L.529
κ=± j+
1 2
h ¯. 1 1 1 1 1 1 1 1 ( + 1) = (j ± )(j + 1 ± ) = j 2 + j ± j ± j ± + = j 2 + j ± j ± + 2 2 2 2 2 4 2 4 It is correct. σ·L+h ¯ 0 0 −σ · L − ¯ h 0 −σ · L ψA ψB ψA ψB = h ¯ = h ¯ (±(j + 1 )ψA 2 (±(j + 1 )ψB 2 (±(j + (±(j +
1 2 1 2
σ·L 0
∓ 1)ψA ± 1)ψB
σ·L
ψA ψB
=h ¯
(±(j + (∓(j +
1 2 1 2
∓ 1)ψA ± 1)ψB
L2
ψA ψB
= = = = =
j(j + 1)¯ 2 h h2 ¯ h2 ¯ h2 ¯ h2 ¯
ψA ψB 3 4
3 4 3 4
− ¯2 h
(±(j + (∓(j + −
1 2 1 2
1 2 1 2
∓ 1)ψA ± 1)ψB
1 2 1 2
3 h − ¯2 4
ψA ψB
j(j + 1) − (j(j + 1) − (j(j + 1) −
ψA ψB ∓ (j + ± (j +
1 2 1 2 1 2 1 2
(±(j + (∓(j +
∓ 1)ψA ± 1)ψB
∓ 1))ψA ± 1))ψB
(j 2 + j ∓ j ∓ (j 2 + j ± j ± (j 2 + j ∓ j ∓ (j 2 + j ± j ±
+ 1 − 3 )ψA 4 + 1 − 3 )ψB 4 + 1 )ψA 4 + 1 )ψB 4
Note that the eigenvalues for the upper and lower components have the same possible values.
cσ · p
ψB ψA
=
E − V (r) − mc2 0
0 E − V (r) + mc2
ψA ψB
We can use commutation and anticommutation relations to write σ ·p in terms of separate angular and radial operators.530
L2
ψA ψB
= h2 ¯
±
+ 1)ψA ( ± + 1)ψB ± 1 =j± 2
∓( ∓
Now we apply the Dirac equation and try to use our operators to help solve the problem. ˆ ˆ σi xi σj xj σn pn σn pn = σi σj xi xj σn pn = ˆ ˆ = = = = 1 1 (σi σj + σj σi )ˆi xj σn pn = 2δij xi xj σn pn = σn pn xˆ ˆ ˆ 2 2 1 σi xi 1 σi xi 1 (σj σn xj pn ) = (σj σn xj pn + σn σj xn pj ) σi xi σj xj σn pn = ˆ ˆ r r r r 2 1 σi xi 1 1 σi xi 1 (σj σn xj pn + (σj σn + 2i njk σk )xn pj ) = ( (σj σn xj pn + σj σn xn pj ) + i njk σk xn pj ) r r 2 r r 2 1 σi xi 1 1 σi xi 1 ( (σj σn xj pn + σn σj xj pn ) + iσk njk xn pj ) = ( (σj σn + σn σj )xj pn + iσk Lk ) r r 2 r r 2 1 σi xi 1 1 σi xi ( 2δjn xj pn + iσk Lk ) = (xj pj + iσk Lk ) r r 2 r r
. ∂ ie mc + γμ Aμ + ∂xμ h ¯c h ¯ mc ∂ ∂ ie + γ4 + γ4 iA0 + γi ∂xi ∂x4 h ¯c h ¯ ∂ ∂ e e mc2 + − iγ4 − γ4 cγi ∂xi ∂t h ¯r h ¯ ∂ ∂ − i¯ + V (r) + mc2 γ4 h h ¯ cγ4 γi ∂xi ∂t ∂ ∂ h ¯ cγ4 γi ψ = i¯ − V (r) − mc2 γ4 h ∂xi ∂t ∂ ∂ 1 0 0 −iσi ψ = i¯ − V (r) − mc2 γ4 h 0 −1 iσi 0 ∂xi ∂t ∂ ∂ 0 −i¯ σi h c ψ = i¯ − V (r) − mc2 γ4 h −i¯ σi h 0 ∂xi ∂t 0 i¯ ∂t − V (r) − mc2 h∂ ψA = ψB 0 i¯ ∂t − V (r) + mc2 h∂ γμ σi pi 0 ψA ψB = E − V (r) − mc2 0 0 E − V (r) + mc2 ψ=0 ψ=0 ψ=0 ψ=0 ψ=0 ψ=0 ψ=0 ψA ψB ψA ψB
h ¯c
c
0 σi pi c
σi pi 0 0 σi pi
The Dirac Equation then is.
σ·x is a pseudoscalar operator. It therefore changes parity and the parity of the state is given r by (−1) . There r are no radial derivatives so they commute with −i¯ r ∂r . These have quantum numbers j.mj − 1 χ+ + βY A . the factor is −1. For either. as is clear from the derivation above. so it must change . and . σ · L is related to K. σ · x mj mj Yj A = −Yj B r
2
. indicating why the full spinor is not an eigenstate of L2 . σ · x mj mj Yj A = eiδ Yj B r m The phase factor depends on the conventions we choose for the states Yj j . Following the notation of Sakurai. ψA has = j + 1 .531 1σ·x r r ∂ + iσ · L ∂r
σ·p
=
−i¯ r h
σ·p=
1σ·x r r
−i¯ r h
∂ + iσ · L ∂r
Note that the operators σ·x and iσ · L act only on the angular momentum parts of the state. we mj will call the state jmj A ≡ Yj A = αY A . so we know the eﬀect of r this operator up to a phase factor. σ · x mj mj Yj A = CYj B r The square of the operator σ·x is one. K Kψ (σ · L + h)ψA ¯ σ · LψA (−σ · L − ¯ )ψB h σ · LψB = ¯ σ·L+h 0 0 −σ · L + −¯ h σ·L+h ¯ 0 0 −σ · L − ¯ h ψA ψB =∓ j+ 1 2 h ¯ ψA ψB
= −κ¯ ψ = h = −κ¯ ψA h
= (−κ − 1)¯ ψA h = −κ¯ ψB h = (κ − 1)¯ ψB h
Second. For negative κ. ψA will have = A and ψB must have the other possible value of which we label B . Lets pick a shorthand notation for the angular h ∂ momentum eigenstates we must use.mj + 1 χ− . For positive κ. (Note that our previous functions 2 2 made use of m = m particularly in the calculation of α and β.) c 1σ·x c r r 1σ·x r r ∂ ψB + iσ · L ψA ∂r mj if (r)Yj B ∂ + iσ · L −i¯ r h mj ∂r g(r)Yj A −i¯ r h = = E − V (r) − mc2 0 E − V (r) − mc2 0 0 E − V (r) + mc2 0 E − V (r) + mc2 ψA ψB
j g(r)Yj A mj if (r)Yj B
m
The eﬀect of the two operators related to angular momentum can be deduced. ψA has = j − 1 . For our conventions. First. mj . ψB has 2 2 the opposite relation for .
c ∂ + iσ · L −i¯ r h ∂r ⎛ h ∂ 1 σ · x ⎝ −i¯ r ∂r + iσ · L c r r −i¯ r ∂r + iσ · L h ∂ 1σ·x r r
j if (r)Yj B mj g(r)Yj A
m
= ⎞ ⎠ =
E − V (r) − mc2 0 E − V (r) − mc2 0 E − V (r) − mc2 0
0 E − V (r) + mc2 0 E − V (r) + mc2 0 E − V (r) + mc2
j g(r)Yj A mj if (r)Yj B j g(r)Yj A mj if (r)Yj B j g(r)Yj A mj if (r)Yj B
m
if (r)Yj g(r)Yj
m
mj
B
m
mj
A
1σ·x c r r
j h h ∂ ¯ r ∂r − (κ − 1)¯ f (r)Yj B mj h −i¯ r ∂r + i(−κ − 1)¯ g(r)Yj A h ∂ 1σ·x h ¯c r r
m
=
j ∂ r ∂r − (κ − 1) f (r)Yj B mj ∂ −ir ∂r − i(1 + κ) g(r)Yj A mj ∂ −r ∂r + (κ − 1) f (r)Yj A 1 h ¯c mj ∂ r ir ∂r + i(1 + κ) g(r)Yj B ∂ 1 −r ∂r + (κ − 1) f (r) h ¯c ∂ r ∂r + (1 + κ) g(r) r ⎛ ⎞ − ∂f + (κ−1) f ∂r r ⎠ h ¯c ⎝ ∂g + (1+κ) g ∂r r
m
= = = =
E − V (r) − mc2 0 E − V (r) − mc2 0 E − V (r) − mc2 0 (E − V − mc2 )g (E − V + mc2 )f
0 E − V (r) + mc2 0 E − V (r) + mc2 0 E − V (r) + mc2
j g(r)Yj A mj if (r)Yj B mj g(r)Yj A mj if (r)Yj B
m
g(r) f (r)
This is now a set of two coupled radial equations.532 We now have everything we need to get to the radial equations.
∂F ∂r ∂G ∂r ∂F ∂ρ ∂G ∂ρ ∂ ∂ρ ∂ ∂ρ
⎛ ⎝ ⎛ ⎝
− +
κF r κG r
− + − +
κF ρ κG ρ κ ρ κ ρ
⎞
= ⎛
k2 − k1 +
k2 k1 k1 k2
Zα r Zα r Zα ρ Zα ρ
G F G
⎠=⎝ F− G−
k2 k1 k1 k2
− +
⎞ ⎠
− +
Zα ρ Zα ρ
F ⎞ ⎠=0
G F
. The extra term from the derivative cancels the 1’s that are with κs. We can simplify them a bit by making the substitutions F = rf and G = rg. The equations then become. Now it is time to specialize to the 2 2 V +E −E hydrogen atom for which hc = − Zα . We deﬁne k1 = mchc and k2 = mchc and the dimensionless ¯ r ¯ ¯ √ ρ = k1 k2 r. h ¯c
1 F F − r ∂F + r2 + κF − r2 ∂r r2 1 ∂G G G κG r ∂r − r 2 + r 2 + r 2 − ∂F + κF ∂r r h ¯c ∂G κG ∂r + r
= =
(E − V − mc2 ) G r (E − V + mc2 ) F r (E − V − mc2 )G (E − V + mc2 )F
∂F ∂r ∂G ∂r
− +
κF r κG r
=
mc2 −E+V hc ¯ mc2 +E−V hc ¯
G F
These equations are true for any spherically symmetric potential.
This means that we look at the m = −1 recursion relations with am = bm = 0 and solve the equations. we will postulate a solution of the form F = e−ρ ρs G = e−ρ ρs
∞ m=0 ∞ m=0
am ρm = e−ρ bm ρm = e−ρ
∞
am ρs+m
m=0 ∞
bm ρs+m .
m=0
The exponential will make everything go to zero for large ρ if the power series terminates.533 With the guidance of the nonrelativistic solutions. and s. we need to have a solution without lower powers. We now substitute these postulated solutions into the equations to obtain recursion relations. We need to verify that this is a solution near ρ = 0 if we pick the right a0 . (s − κ)a0 + Zαb0 = 0 −Zαa0 + (s + κ)b0 = 0 (s − κ) Zα −Zα (s + κ) a0 b0 =0
s2 − κ2 + Z 2 α2 = 0
. b0 . ∂ κ − ∂ρ ρ ∂ κ + ∂ρ ρ
∞
F− G−
k2 Zα − k1 ρ k1 Zα + k2 ρ
G=0 F =0
−am ρs+m + am (s + m)ρs+m−1 − am κρs+m−1 − bm
m=0 ∞
k2 s+m ρ + bm Zαρs+m−1 k1 k1 s+m ρ − am Zαρs+m−1 k2 k2 + bm+1 Zα k1 k1 − am+1 Zα k2
=0
−bm ρs+m + bm (s + m)ρs+m−1 + bm κρs+m−1 − am
m=0
=0
−am + am+1 (s + m + 1) − am+1 κ − bm −bm + bm+1 (s + m + 1) + bm+1 κ − am −am + (s + m + 1 − κ)am+1 − −bm + (s + m + 1 + κ)bm+1 −
=0 =0
k2 bm + Zαbm+1 = 0 k1 k1 am − Zαam+1 = 0 k2
−am + (s + m + 1 − κ)am+1 − −
k2 bm + Zαbm+1 = 0 k1
k1 am − Zαam+1 − bm + (s + m + 1 + κ)bm+1 = 0 k2
For the lowest order term ρs .
We can then take the equations in the coeﬃcients and set anr +1 = bnr +1 = 0 to get relationships between anr and bnr . −am + (s + m + 1 − κ)am+1 − − k2 bm + Zαbm+1 = 0 k1 =0 =0 =0 =0 =0
−
k1 am − Zαam+1 − bm + (s + m + 1 + κ)bm+1 k2 k2 −anr −1 + (s + nr − κ)anr − bn −1 + Zαbnr k1 r k1 − an −1 − Zαanr − bnr −1 + (s + nr + κ)bnr k2 r k1 k1 k1 an −1 + (s + nr − κ) an − bnr −1 + Zα bn k2 r k2 r k2 r k1 an −1 − Zαanr − bnr −1 + (s + nr + κ)bnr − k2 r
At this point we take the diﬀerence between the two equations to get one condition. anr = − bnr = − k2 bn k1 r k1 an k2 r
These are the same equation. This can be seen approximately by assuming either the a’s or the b’s are small and noting that the series is that of a positive exponential. Note that this choice of m connects anr and bnr to the rest of the series giving nontrivial conditions on E. s=+ κ2 − Z 2 α2
As usual. The ﬁnal step is to use this result in the recursion relations for m = nr − 1 to ﬁnd a condition on E which must be satisﬁed for the series to terminate. We need to take the positive root in order to keep the state normalized. Assume the series for F and G terminate at the same nr . We already have the information from the next step in the recursion which gives anr +1 = bnr +1 = 0. Z 2 α2 is a small noninteger number.534 s2 = κ2 − Z 2 α2 s = ± κ2 − Z 2 α2 Note that while κ is a nonzero integer. the series must terminate at some m = nr for the state to normalizable. which is consistent with our assumption. (s + nr − κ) −(s + nr − κ) k1 + Zα anr + k2 k2 bn + k1 r Zα Zα k1 − (s + nr + κ) bnr = 0 k2 k1 − (s + nr + κ) bnr = 0 k2
k1 − Zα k2
.
we have solved the radial equation in a similar way as for the nonrelativistic case yielding the exact energy relation for relativistic Quantum Mechanics.
E= 1+
nr +
mc2
Z 2 α2
(j+ 1 )2 −Z 2 α2 2
2
We can identify the standard principle quantum number in this case as n = nr + j + 1 .
. Relativistic corrections become quite important for high Z atoms in which the typical velocity of electrons in the most inner shells is of order Zαc. This result gives 2 the same answer as our nonrelativistic calculation to order α4 but is also correct to higher order. such as the Lamb shift and the anomalous magnetic moment of the electron.535
−(s + nr − κ) − Zα
k2 + Zα k1
k1 − (s + nr + κ) = 0 k2 k1 k2 + Zα(k1 − k2 ) = 0 k1 k2 = Zα(k1 − k2 ) m2 c4 − E 2 = 2ZαE
−(s + nr − κ) k1 k2 − Zαk2 + Zαk1 − (s + nr + κ) k1 k2 = 0 −2(s + nr ) 2(s + nr ) 2(s + nr )
(s + nr ) m2 c4 − E 2 = ZαE (s + nr )2 (m2 c4 − E 2 ) = Z 2 α2 E 2 (s + nr )2 (m2 c4 ) = (Z 2 α2 + (s + nr )2 )E 2 (s + nr )2 (m2 c4 ) = E 2 ((s + nr )2 + Z 2 α2 ) m 2 c4 E2 = Z 2 α2 (1 + (s+nr )2 ) E= mc2 1+ E= 1+
nr + Z2 2 √ α (nr + κ2 −Z 2 α2 )2
mc2 1+
Z 2 α2 (nr +s)2
E=
mc2
Z 2 α2
(j+ 1 ) 2
2
−Z 2 α2
2
Using the quantum numbers from four mutually commuting operators. It is an exact solution to the quantum mechanics problem posed but does not include the eﬀects of ﬁeld theory.
Now lets take a look at one of the matrix elements.2
p r iγ4 γn n e−ik ·x p r p r iγ4 γn n eik·x pr E − E − ¯ω h
ne −ik ·x
+
p r iγ4 γn n eik·x p r p r iγ4 γn E − E + hω ¯
pr
t
i h ¯
0
dt2 ei(E
−E+¯ ω −¯ ω)t2 /¯ h h h
As in the earlier calculation.α e
+
(α ) † n ak . 2. the photon states have been eliminated from the equation since they give a factor of 1 with the initial state photon being annihilated and the ﬁnal state photon being created in each term. we have only one term in the interaction Hamiltonian.α
ei(−k·x+ω t2 ) )I ei(E
−E )t2 /¯ h
×
0 (2) (t) p . In the Dirac theory.k .r . as are the intermediate electron states.
(2) (t) c p .α
kα
The initial and ﬁnal states are deﬁnite momentum states. Hint = ieγ4 γk Ak Because it is linear in A it can create a photon or annihilate a photon. γi = 0 iσi −iσi 0
(r )†
γ4 γn u0
(r)
= 0. We shall ﬁrst do the calculation assuming no electrons from the “negative energy” sea participate. There is no A2 term so we are just computing the two second order terms. Photon scattering is therefore second order (and proportional to e2 ). The quantized photon ﬁeld is 1 Aμ (x) = √ V h ¯ c2 2ω
(α) μ
ak. k ˆ(α ) iγ4 γn (
0
(α) i(k·x−ωt2 ) n ak. It turns out that u0 that the cross section is zero in this limit. The intermediate states must also be positive energy states since the “negative energy” states are all ﬁlled.α (0)eikρ xρ + a† (0)e−ikρ xρ .α
ei(−k·x+ω t1 ) )pr. Recall that we got the correct cross section from the nonrelativistic calculation and that Thomson also got the correct result from classical E&M.r . k. ˆ
=
−e2 h ¯2
t2
I
h 1 ¯ c2 √ V 2 ωω
−E)t1 /¯ h
t
dt2 p r . so
. The initial and ﬁnal (r) states are therefore the positive energy plane wave states ψp for r = 1. a delta function requires that p = 0.16
Thomson Scattering
The cross section for Thomson scattering illustrates the need for “negative energy” states in our calculations. The computation of the scattering cross section follows the same steps made in the development of the KrammersHeisenberg formula for photon scattering. Assume the initial state electron is at rest and that the photon momentum is small.k ˆ
dt1 ei(E h e 2 ¯ c2 √ 2V ω ω
Iiγ4 γn (
(α) i(k·x−ωt1 ) n ak. kˆ(α)
c
=
p r =1.α e
+
(α ) † n ak . p r iγ4 γn n eik·x pr For p = 0 and k = 0.536
35. other than to exclude transitions to those “negative energy” states.
These terms are larger because the γ4 γi matrix connects positive energy and “negative energy” states. a “negative energy” electron emits the ﬁnal state photon and moves to a positive energy state. 2 spinors to r = 3. In fact.
. then the initial state electron absorbs the initial photon and ﬁlls the hole left behind in the sea. there is a small contribution.
In one term. In the other term.r . the ﬁnal electron h (approximately) at rest. due to a delta function of momentum conservation that comes out of the spatial integral.537 1 0 0 −1 −iσi 0
γ4 γ4 γi
= =
0 −iσi
This matrix only connects r = 1. since the photon momentum is not quite zero. There are additional terms if we consider the possibility that the photon can elevate a “negative energy” electron to have positive energy. ¯ k << mc.k ˆ
=
ie2 c2 √ 2V ω ω
p r =3. then the initial state electron ﬁlls the hole in the “negative energy” sea emitting the ﬁnal state photon. The above calculation misses some important terms due to the “negative energy” sea. the initial state photon is absorbed by a “negative energy” electron. but far too small. c
(2) (t) p . So. 4 spinors because of its oﬀ diagonal nature. even further from the mass shell. and hence the intermediate electron at rest. the calculation yields zero for a cross section in contradiction to the other two calculations.4
p r iγ4 γn n e−ik ·x pr p r iγ4 γn n eik·x p r E − E − ¯ω h
ne −ik ·x
+
p r iγ4 γn n eik·x pr p r iγ4 γn E − E + hω ¯
p r
0
t
dt2 ei(E
−E+¯ ω −¯ ω)t2 /¯ h h h
The matrix element is to be taken with the initial electron at rest.
r .r .r .r .4 −E+¯ ω −¯ ω)t2 /¯ h h h
)†
σ · ˆ χ(r) ) + (χ(r )† σ · ˆ χ(r ) )(χ(r
)†
σ · ˆχ(r) )
dt2 ei(E
0
(2) c (t) p . γ4 γi u0
(r )†
= = =
0 −iσi 0.r .r .k ˆ
=
ie2 √ χ(r )† (σ · ˆ)(σ · ˆ ) + (σ · ˆ )(σ · ˆ) χ(r) 4mV ω ω ie2 √ χ(r )† [σi σj + σj σi ] ˆi ˆ j χ(r) 4mV ω ω ie2 √ χ(r )† ˆ · ˆ χ(r) 2mV ω ω ie √ ˆ · ˆ δrr 2mV ω ω e2 2mV
2 2 t t t
t
dt2 ei(E
0
−E+¯ ω −¯ ω)t2 /¯ h h h
c
(2) (t) p .k ˆ
=
dt2 ei(E
0
−E+¯ ω −¯ ω)t2 /¯ h h h
c
(2) (t) p .k ˆ (t)
(2)
=
ie2 √ 4mV ω ω
t
(χ(r )† σ · ˆχ(r ) )(χ(r
r =3.k ˆ
ie2 √ 4mV ω ω
t
[ 0r iγ4 γn
r =3.538 Let the positive energy spinors be written as u0 = and the “negative energy” spinors as u0
(r ) (r)
χ(r) 0
=
0 χ(r
)
The matrix γ4 γi connect the positive and “negative energy” spinors so that the amplitude can be written in terms of two component spinors and Pauli matrices.r .4
)†
σ · ˆ χ(r) )(χ(r )† σ · ˆχ(r ) ) + (χ(r
)†
σ · ˆχ(r) )(χ(r )† σ · ˆ χ(r ) )
dt2 ei(E
0
−E+¯ ω −¯ ω)t2 /¯ h h h
cp .k ˆ
=
dt2 ei(E
0
−E+¯ ω −¯ ω)t2 /¯ h h h
c
(2) (t)2 p .k ˆ
=
ie2 √ 4mV ω ω
t
(χ(r
r =3.k ˆ
=
1 ˆ · ˆ 2 δrr 2πtδ(E /¯ − E/¯ + ω − ω) h h ωω
.r .k ˆ
=
dt2 ei(E
0
−E+¯ ω −¯ ω)t2 /¯ h h h
c
(2) (t) p . χ(r
−iσi 0
)†
iγ4 γi u0
(r)
0 σi
σi 0
χ(r) 0
= χ(r
n 0r
)†
σi χ(r) + 0r iγ4 γn n 0r 0r iγ4 γn n 0r ]
c
(2) (t) p .4 −E+¯ ω −¯ ω)t2 /¯ h h h
0r iγ4 γn n 0r
dt2 ei(E
0
c
(2) (t) p .
35. the tables assume the momentum is along the z direction so that we can have spin up and spin down eigenstates. due the product of three signs. The hole also has positive energy compared to the vacuum since it is lacking the negative energy present in the vacuum state. The electron and positron have opposite charge so the standard Electromagnetic currents are in opposite directions.
spin up. The tables below compare an electron and a positron with the same momentum and spin. “negative energy” electron
charge −e +e −e
mom. pˆ z pˆ z −pˆ z
Energy + p 2 c2 + m 2 c4 + p 2 c2 + m 2 c4 − p 2 c2 + m 2 c4
Sz ¯ +h 2 h +¯ 2
¯ −h 2
j (EM) −ˆ z +ˆ z −ˆ z
v +ˆ z +ˆ z +ˆ z
spinor u(1) (p) v (1) (p) −u(4) (−p)
. The last row of the table shows the “negative energy” electron state that must be unoccupied to produce the positron state shown in the row above it. This describes the process of pair creation. Because the probability ﬂux for the “negative energy” electron states is in the opposite direction of the momentum. Energy would be given oﬀ. The same result could be obtained with the possibility of pair creation. positive energy positron (spin down “negative energy” hole) spin down. For simplicity. momentum.539 e2 2mV e2 2mcV e2 2mcV e2 4πmc2
2
Γ Γ dσ dΩ dσ dΩ
= = = =
2π ωω
2
V k 2 dk dΩ ˆ · ˆ 2 δrr δ(ω − ω) (2π)3 V dΩ ˆ · ˆ 2 δrr (2π)3
2π
2
1 c
2π
2
V 1 V ˆ · ˆ 2 δrr c c (2π)3
ˆ · ˆ 2 δrr
This agrees with the other calculations and with experiment. again with the hypothesis that a positron is a “negative energy” electron going backward in time. positive energy electron spin up. This is the process of pair annihilation. Therefore. Eﬀectively we are allowing for the creation of electron positron pairs through the use of the ﬁlled negative energy states. The “negative energy” sea is required to get the right answer in Dirac theory. This would yield a positive energy electron plus a hole in the “negative energy” sea. any positive energy electron could make a transition to the now empty “negative energy” state. There are alternatives to the “negative energy” sea.17
Hole Theory and Charge Conjugation
Dirac postulated that the “negative energy” sea was entirely ﬁlled with electrons and that an antielectron would be formed if one of the “negative energy” electrons were elevated to a positive energy state. This means the velocities are in the same direction. Similarly. both the electron and the positron would have positive energy. A hole in the vacuum naturally produces a positron of opposite charge. (and the charge and momentum are opposite the positron) the EM current of the positron and of the “negative energy” state are in opposite directions. for example by the emission of two photons. and spin. and the system would return to the vacuum state.
(Assume the equation. for the spin down positron. − Aμ γμ SC ψ ∗ + ∂xμ h ¯c h ¯ Take the complex conjugate carefully remembering that x4 and A4 will change signs. the Dirac equation also has a symmetry under charge conjugation. ie ∂ ie mc ∗ ∂ ∗ ∗ ∗ ∗ S ψ=0 + Ai γi SC ψ + − − A4 γ4 SC ψ + ∂xi h ¯c ∂x4 h ¯c h ¯ C
. positive energy electron spin down. Note that the minus sign on u(4) is conventional and will come from our future deﬁnition of the charge conjugation operator. The charge conjugate equation then is ie mc ∂ SC ψ ∗ = 0.
35. First of all. “negative energy” electron
charge −e +e −e
mom. Similarly we can make a table starting from a spin down electron. c ∂ mc ψ=0 γμ ψ + ∂xμ h ¯ ∂ ie mc ψ=0 + Aμ γμ ψ + ∂xμ h ¯c h ¯ The strategy is to try to write the charge conjugate of this equation then show that it is equivalent to the Dirac equation with the right choice of charge conjugation operator for ψ.) Second assume. including the constant e is the same but the sign of the EM ﬁeld Aμ changes. that the Dirac spinor is transformed to its charge conjugate by the operation ψ C = SC ψ ∗ where we are motivated by complex scalar ﬁeld experience. positive energy positron (spin up “negative energy” hole) spin up. SC is a 4 by 4 matrix. We wish to write the Dirac equation in a way that makes the symmetry between electron and positron clear. v (2) . boost and parity symmetry. pˆ z pˆ z −pˆ z
Energy + p 2 c2 + m 2 c4 + p 2 c2 + m 2 c4 − p 2 c2 + m 2 c4
Sz ¯ −h 2 h −¯ 2
¯ +h 2
j (EM) −ˆ z +ˆ z −ˆ z
v +ˆ z +ˆ z +ˆ z
spinor u(2) (p) v (2) (p) u(3) (−p)
We have now also deﬁned the spinor.540 We have deﬁned the positron spinor v (1) to be the one with positive momentum and spin up. for now. the sign of eAμ is expected to change in the charge conjugate equation. Start from the Dirac equation and include the coupling to the EM ﬁeld with the substitution that p → p + e A .
spin down. in addition to rotation.18
Charge Conjugate Waves
Assume that.
541
∗−1 Multiply from the left by SC . ψp = ψp = ψp = ψp =
(4) (3) (2) (1)
mc2 (1) i(p·x−Et)/¯ h u e EV p mc2 (2) i(p·x−Et)/¯ h u e EV p mc2 (3) i(p·x+Et)/¯ h u e EV p mc2 (4) i(p·x+Et)/¯ h u e EV p
→ − → → → −
mc2 (4) i(−p·x+Et)/¯ h u e ≡ EV −p mc2 (3) i(−p·x+Et)/¯ h u e ≡ EV −p mc2 (2) i(−p·x−Et)/¯ h u e EV −p mc2 (1) i(−p·x−Et)/¯ h u e EV −p
mc2 (1) i(−p·x+Et)/¯ h v e EV p mc2 (2) i(−p·x+Et)/¯ h v e EV p
.sign.
⎛
It anticommutes with γ1 and γ3 producing a minus sign to cancel the one from complex conjugation. Applying this to the plane wave solutions gives. The solution in our representation (only) is
∗−1 −1 ∗ SC = SC = SC = SC = γ2 .
ψ = γ2 ψ ∗
Of course a second charge conjugation operation takes the state back to the original ψ. ⎞ ⎛ ⎞ ⎛ ⎞ ⎛ ⎞ 0 0 0 −i 0 0 0 −1 0 0 −i 0 1 0 0 0 0 i⎟ 0 ⎟ ⎜ 0 0 −i 0 ⎟ ⎜ 0 0 1 0 ⎟ ⎜0 0 ⎜0 1 0 γ1 = ⎝ ⎠ γ2 = ⎝ ⎠ γ3 = ⎝ ⎠ γ4 = ⎝ ⎠ 0 i 0 0 0 1 0 0 i 0 0 0 0 0 −1 0 i 0 0 0 −1 0 0 0 0 −i 0 0 0 0 0 −1 note that γ1 and γ3 are completely imaginary and will change sign upon complex conjugation. The charge conjugate of the Dirac spinor is given by. It commutes with γ2 giving the right + sign. while γ2 and γ4 are completely real and will not. ∂ ie + Aμ γμ ψ + ∂xμ h ¯c ∂ ie + A4 γ4 ψ + γi ψ + ∂x4 h ¯c mc ψ=0 h ¯ mc ψ=0 h ¯
∂ ie + Ai ∂xi h ¯c
The two equations will be the same if the matrix SC satisﬁes the conditions. It anticommutes with γ4 giving the right .
∂ ie ∂ ie mc ∗−1 ∗ ∗ ∗−1 ∗ ∗ ψ=0 + Ai SC γi SC ψ + − − A4 SC γ4 SC ψ + ∂xi h ¯c ∂x4 h ¯c h ¯ Compare this to the original Dirac equation.
Recalling the γ matrices in our representation.
∗−1 ∗ ∗ SC γi SC = γi ∗−1 ∗ ∗ SC γ4 SC = −γ4 .
because the sign of the Et term in the exponential is reversed. with the right momentum and spin. Let us take one more look at a plane wave solution to the Dirac equation. That is.
t3
t2 t1
. At time t3 . the ﬁeld transition to causes the creation of an electron positron pair both of which propagate forward in time. Assume that we have found a new solution to the ﬁeld equations that moves backward in time rather than forward. at time t2 . it behaves as a positive energy solution moving backward in time. spin. The electron produced at t2 propagates on into the future. From one point of view. the electron starts out at t1 . Discard the idea of the “negative energy” sea. momentum. the conjugate is the hole needed to make a positron with the same properties as the electron except that it has opposite charge. These solutions behave like antiparticles moving forward in time. the positron and initial electron annihilate interacting with the ﬁeld.542 The charge conjugate of an electron state is the “negative energy” electron state. and spin opposite to the original state. opposite momentum −p. At time t3 . Our opinion of the “negative energy” solutions has been biased by living in a world of matter. Consider the following diagram (which contributes to Thomson scattering) from two points of view. the absence of which would produce a positron of the same energy. ψp =
(1) (1)
mc2 (1) i(p·x−Et)/¯ h u e EV p
→ −
mc2 (4) i(−p·x+Et)/¯ h u e ≡ EV −p
mc2 (1) i(−p·x+Et)/¯ h v e EV p
The charge conjugate of the electron solution is an electron with the same charge −e. the electron interacts with the ﬁeld and makes a transition to the state ψ
(1) ψp . then. There is a symmetric set of solutions for h the same particles moving “backward in time” oscillating as ei(−p·x+Et)/¯ . an electron (1) starts out at t1 . lets say in the state ψp . from the point of view that a positron is an electron moving backward in time. and velocity as the electron. It satisﬁes the equation with the signs of the EM ﬁelds reversed and. for example ψp and its charge conjugate. We know h about matter waves oscillating as ei(p·x−Et)/¯ . (4) p
which travels backward in time to t2 where it again interacts and makes a
From the other point of view.
19
Quantization of the Dirac Field
The classical free ﬁeld Lagrangian density for the Dirac electron ﬁeld is. The EulerLagrange ¯ ¯ equation using the ψ independent ﬁelds is simple since there is no derivative of ψ in the Lagrangian. The charge conjugate solution is that of an electron going backward in time that can also be treated as a positron going forward in time. A parity operation changes the system to a symmetric one that also satisﬁes the equations of motion but is diﬀerent from the original system. The charge conjugation operation is similar to parity. ∂ ∂xμ ∂L ∂(∂ψ/∂xμ ) − ∂L ∂ψ = 0
∂ ¯ −c¯ ψγμ + mc2 ψ = 0 h¯ ∂xμ mc ¯ ∂ ¯ ψ = 0 ψγμ + − ∂xμ h ¯ again indicating that this is the correct Lagrangian if the Dirac equation is assumed to be correct. we start by ﬁnding the momenta conjugate to the ﬁelds ψ. To compute the Hamiltonian density.
35. No change in the “negative energy” solutions is needed although it will be helpful to relabel them with the properties of the positron rather than the properties of the electron moving backward in time.543 No reference to the “negative energy” sea is needed. The EulerLagrange equation derived using the ﬁelds ψ is the Dirac adjoint equation. ∂ ¯ L = −c¯ ψγμ h¯ ψ − mc2 ψψ ∂xμ ¯ The independent ﬁelds are considered to be the 4 components of ψ and the four components of ψ. ∂ ∂xμ ∂L ¯ ∂(∂ ψ/∂xμ ) − ∂L ¯ =0 ∂ψ
∂L =0 ¯ ∂(∂ ψ/∂xμ ) ∂L ¯ =0 ∂ψ −c¯ γμ h ∂ ψ − mc2 ψ = 0 ∂xμ ∂ mc + γμ ψ=0 ∂xμ h ¯
This gives us the Dirac equation indicating that this Lagrangian is the right one. Π= ∂ ∂L
∂ψ ∂t
= −c¯ ψγ4 h¯
1 = i¯ ψ † γ4 γ4 = i¯ ψ † h h ic
. This Lagrange density is a Lorentz scalar that depends only on the ﬁelds. Both parity and charge conjugation are good symmetries of the Dirac equation and of the electromagnetic interaction.
2.r up δpp E
.r p
Writing the Hamiltonian in terms of these ﬁelds.r p
mc2 (r) h cp.r p
mc2 (r) h cp.
4
ψ(x.r p h ¯ mc2 ∗ (r )† −i(p·x−Et)/¯ h c icγ4 γk pk + mc2 γ4 u e E V p .r up ei(p·x−Et)/¯ d3 x EV mc2 (r) h cp.544 ¯ There is no time derivative of ψ so those momenta are zero. the formula can be simpliﬁed as follows H H = =
p r=1 p 4 r =1 4
ψ † ¯ cγ4 γk h
4
∂ + mc2 γ4 ψd3 x ∂xk
4
mc2 ∗ ∂ (r )† −i(p·x−Et)/¯ h c u e + mc2 γ4 h ¯ cγ4 γk E V p . The Hamiltonian can then be computed.r p ∂xk mc2 ∗ ipk (r )† −i(p·x−Et)/¯ h c + mc2 γ4 u e h ¯ cγ4 γk E V p . t) =
p r=1
mc2 (r) h cp.
4
ψ † (x.r up ei(p·x−Et)/¯ d3 x EV
H
=
p r=1 p 4 r =1 4
H
=
p r=1 p r =1
icγ4 γj pj + mc2 γ4 ψ = Eψ
4 4
H
=
p r=1 p r =1
mc2 ∗ (r )† −i(p·x−Et)/¯ h c u e (E) E V p . For economy of notation. 3. 4 or using the electron and positron spinors up and vp for r = 1. 2.r up ei(p·x−Et)/¯ d3 x EV
4
4
H
=
p r=1 p r =1
mc2 ∗ (r )† c u (E) E  p . t) =
p r=1
mc2 ∗ (r)† −i(p·x−Et)/¯ h c u e EV p.r up ei(p·x−Et)/¯ d3 x EV mc2 (r) h cp. we choose the former with a plan to change to the later once the quantization is completed. H = = = = = H = ∂ψ Π−L ∂t ∂ψ ∂ ¯ + c¯ ψγμ h¯ i¯ ψ † h ψ + mc2 ψψ ∂t ∂xμ ∂ψ ∂ψ ∂ ¯ + c¯ ψ † γ4 γ4 h + c¯ ψγk h¯ ψ + mc2 ψψ −c¯ ψ † h ∂x4 ∂x4 ∂xk ∂ ψ + mc2 ψ † γ4 ψ hcψ † γ4 γk ¯ ∂xk ∂ ψ † ¯ cγ4 γk h ψ + mc2 γ4 ψ ∂xk ∂ ψ † ¯ cγ4 γk + mc2 γ4 ψd3 x h ∂xk
We may expand the ﬁeld ψ in the complete set of plane waves either using the four spinors up
(r) (r)
(r)
for r = 1.r up ei(p·x−Et)/¯ EV
The conjugate can also be written out.r p
mc2 (r) cp.
r cp.α k.α k. H = 1 2 h ¯ ω ak.r up (E) up E p.α c∗ k.α a† + a† ak.α
The Hamiltonian written in terms of the creation and annihilation operators is.α k. we can skip the steps of making coordinates and momenta for the individual oscillators. and just replace the Fourier coeﬃcients for the Dirac plane waves by operators.r
where previous results from the Hamiltonian form of the Dirac equation and the normalization of the Dirac spinors have been used to simplify the formula greatly. Compare this Hamiltonian to the one used to quantize the Electromagnetic ﬁeld H=
k.α
ω c
2
ck.α
for which the Fourier coeﬃcients were replaced by operators as follows.α 2ω h ¯ c2 † a 2ω k.α c∗ + c∗ ck.α = = h ¯ c2 ak.r E δrr mc2
up H =
p
(r)†
up
4
(r ) 4
=
r=1 r =1 4
mc2 E ∗ E cp.α
k.) The creation an annihilation operators bp {bp .r p.545
4 4
H
=
p r=1 r =1
mc2 ∗ (r )† (r) c cp. t) =
p r=1
(Since the FermiDirac operators will anticommute.
4
H
=
p r=1 4
E bp
(r)† (r) bp
ψ(x.α k. the analogy is imperfect.r δrr E mc2
H
=
p r=1
E c∗ cp. = δrr δpp
(r)
(r )†
}
. bp
(r) (r)†
and bp satisfy anticommutation relations.α
By analogy. t) =
p r=1 4 †
mc2 (r) (r) i(p·x−Et)/¯ h b up e EV p mc2 (r)† (r)† −i(p·x−Et)/¯ h b up e EV p
ψ (x. ck.
Recall that we can replace −u−p with the positron spinor vp and u−p with vp
(3) (2)
such that the new spinors are charge conjugates of the electron spinors. The state can be generated by operation on the vacuum state with the appropriate set of creation operators. t) =
p s=1 2
H
=
p s=1 2
− dp dp + dp
(s) (s)†
=
p s=1
E bp
(s)† (s) bp
(s)† (s) dp
−1
. A state of the electrons in a system can be described by the occupation numbers (0 or 1 for each plane wave).20
The Quantized Dirac Field with Positron Spinors
The basis states in our quantized Dirac ﬁeld can be changed eliminate the “negative energy” states and (4) (1) replace them with positron states. t) =
p s=1 2
mc2 (s) (s) i(p·x−Et)/¯ (s)† (s) h h bp u p e + dp vp e−i(p·x−Et)/¯ EV mc2 (s)† (s)† −i(p·x−Et)/¯ (s) (s)† h h bp u p e + dp vp ei(p·x−Et)/¯ EV E bp
(s)† (s) bp
ψ † (x. dp
(s) (s )†
} = δss δpp
The Dirac ﬁeld and Hamiltonian can now be rewritten. The anticommutation relations constrain the occupation number to be 1 or 0. 2
The positron spinor is actually just the same as the negative energy spinor when the momentum is reversed. SC u p
(s)∗
= vp
(s)
s = 1. dp dp
(1) (2) (s)†
and dp
(s)
= =
−bp bp
(4)†
(3)†
These anticommute with everything else with the exception that {dp .
2
ψ(x. We name the creation and annihilation operators for the positron states to be dp and identify them to be.
35.546 {bp . bp } {bp
(r)† (r) (r)
†
= 0 = 0 = bp
(r)† (r) bp
. bp
(r)
}
Np
(r)
(r)
Np is the occupation number operator.
Note that. which we must add to make the vacuum state have zero energy. The term Vacuum Polarization is descriptive of the eﬀect. causing a net polarization of the vacuum which screens the nuclear charge. b† } = 0 r r The states are then antisymmetric under interchange of pairs of fermions. the bare charge is seen.
. There is an (inﬁnite) constant energy. A virtual electron positron pair in the vacuum will be aﬀected by the charge. In this case. This eﬀect is actually rather small even compared to the Lamb shift and of opposite sign. there would have been no lowest energy ground state so this Energy subtraction would not have been possible. (iγμ pμ + mc)up = 0 (−iγμ pμ + mc)vp = 0
(s) (s) (s)
Since we changed the sign of the momentum in our deﬁnition of vp . FermiDirac statistics are required for particles satisfying the Dirac equation. Since the operators creating fermion states anticommute. had we used commuting operators (BoseEinstein) instead of anticommuting. The reduction is dependent on distance and hence on the energy scale. A charged particle will polarize the vacuum in a way analogous to the way a dielectric is polarized.21
Vacuum Polarization
Vacuum polarization is an important eﬀect in eﬀectively reducing the charge on a particle. The eﬀect of vacuum polarization on Hydrogen would be to lower the energy of s states relative to others since they are close to the nucleus and therefore see an unscreened charge. Vacuum Polarization has larger eﬀects at higher energies at which shorter distances are probed. This polarization of the vacuum is similar to the polarization of a dielectric material. b† b† 0 = −b† b† 0 r r r r Its not hard to show that the occupation number for fermion states is either zero or one. In fact we can say that the electromagnetic coupling varies slowly with the energy scale. Of course other particles than the electron can be polarized in the vacuum so the energy variation of the coupling “constant” is an interesting subject for research. fermion states must be antisymmetric under interchange. {b† . while at long distances the screening is important. the momentum term in the Dirac equation had to change sign. Assume b† and br are the creation and annihilation operators for fermions and that r they anticommute. the virtual electron will be attracted and the virtual positron repelled.
35. This is referred to as the running of the coupling constant.547 All the energies of these states are positive. Note that the spinors satisfy the following equations. increasing (logarithmically) at higher energies. similar but of opposite sign to the one for the quantized EM ﬁeld. At very short distances from the nucleus. This causes the basic coupling α to vary a bit with distance and therefore with energy. If the original charged source is a nucleus for example. what is being polarized are the virtual electrons and positrons in the vacuum.
The distance the electron appears to jump then is of the order of cΔt = 2mc2 = 0. ∂ mc 1 ¯ + L = −¯ cψ γμ h ¯ ψ − Fμν Fμν − ieψγμ Aμ ψ ∂xμ h ¯ 4 QED is our ﬁrst complete example of an interacting Quantum Field Theory. however.
+
We can estimate the distance an electron might jump as it undergoes this process. The diagram below shows a photon from the Coulomb ﬁeld of the nucleus producing an electron positron pair. The primary diﬀerence between Quantum Mechanics and Quantum Field Theory is that particles can be created and destroyed. coupling to another ﬁeld photon. It can change with time. It taught us a great deal about the laws of physics.α
kα
. The original real electron from the atom then anihillates with the positron. The electron from the pair is left over and becomes the new atomic electron. Aμ = 1 √ V h ¯ c2 2ω
(α) μ
ak.22
The QED LaGrangian and Gauge Invariance
The LaGrangian for electrons. First the time for which the virtual pair exists can be estimated from the uncertainty principle. photons.α (t)eik·x + a† (t)e−ik·x k.
35. it need not be in the same place as the original electron. Energy conservation is h ¯ violated by 2mc2 at least so Δt = 2mc2 (which is approximately the reciprocal of the Zitterbewegung hc ¯ frequency). This is the aproximate size of the fast back and forth motion of Zitterbewegung.548 We can get some qualitative understanding of the origin of Zitterbewegung from the idea of virtual pair production in the ﬁeld of the nucleus. We have written the ﬁelds of the photon and the electron in terms of creation and annihilation operators. and the interaction between the two is the LaGrangian of Quantum ElectroDynamics.002 Angstroms. The probability to ﬁnd an electron or a photon integrated over space does not have to be one.
Remember that electric current in 4D also includes the charge density. We o can deduce from the above transformation that ¯ ¯ ψ → e−iλ(x) ψ ∂ ∂λ(x) ∂ ∂λ(x) − = Fμν ∂xμ ∂xν ∂xν ∂xμ
Fμν =
∂Aν ∂Aμ h ¯c − → Fμν − ∂xμ ∂xν e
The transformed LaGrangian then can be computed easily. This is just a local phase symmetry times an arbitrary local rotation in SU(2) space. we can easily deduce what boson ﬁelds are required to make the LaGrangian gauge invariant. (The
. This can be most directly studied using the LaGrangian. ∂ mc L = −¯ cψ γμ h ¯ + ∂xμ h ¯ 1 ¯ ψ − Fμν Fμν − ieψγμ Aμ ψ 4
¯ The exponentials from ψ and ψ cancel except for the term in which ψ is diﬀerentiated. The SU(2) group is familiar to us since angular momentum is based on SU(2). t) =
p s=1
¯ Note that in the interaction term −ieψγμ Aμ ψ photons can be created or destroyed singly but that electrons must be created and destroyed along with a positron. −m2 Aμ Aμ . This simple transformation ψ → eiλ(x) ψ is called a local U(1) symmetry where the U stands for unitary. The LaGrangian is no longer gauge invariant.549
2
ψ(x. L → L − i¯ cψγμ h ¯ ∂λ h ¯ −¯ c ∂λ ψ = L ψ − ieψγμ ∂xμ e ∂xμ
This all may seem fairly simple but imagine that we add a mass term for the EM ﬁeld. another important result. It turns out we need a triplet of bosons. In the weak interactions. there are two particles that are the symmetric (much like a spin up and a spin down electron but NOT a spin up and spin down electron). We can rotate our states into diﬀerent linear combinations of the symmetric particles and the LaGrangian remains invariant. The Weak interactions are based on an SU(2) symmetry. Gauge invariance implies conservation of charge. Given this local SU(2) symmetry of the fermion wave functions. t) =
p s=1 2
mc2 (s) (s) i(p·x−Et)/¯ (s)† (s) h h bp u p e + dp vp e−i(p·x−Et)/¯ EV mc2 (s)† (s)† −i(p·x−Et)/¯ (s) (s)† h h bp u p e + dp vp ei(p·x−Et)/¯ EV
ψ † (x. Phase (or Gauge) symmetry can be studied very simply from this LaGrangian. Gauge invariance implies zero mass photons and even maintains the massless photon after radiative corrections. Gauge invariance also implies the existence of a conserved current. We have shown that the phase transformation ψ → eiλ(x) ψ h ¯ c ∂λ(x) Aμ → Aμ − e ∂xμ leaves the Schr¨dinger equation invariant.
γ2 ] = 2iΣ3 and γi γj = δij + i γ1 γ2 γ3 γ4 . γ5 } = 2δμ5 with μ = 1. without using an explicit representation for γ5 . Time reversal should be a symmetry of the Dirac equation. Show that this is true. Prove that γ5 is Hermitian and that {γμ .
ijk Σk . So the Standard Model is as simple as 1 2 3 in Quantum Field Theories. What do the operators 1±γ5 project from a Dirac spinor? 2
3.
35.550 weak interactions then get messy because of the Higgs mechanism but the underlying gauge theory is still correct.23
Interaction with a Scalar Field
¯ Yukawa couplings to a scalar ﬁeld would be of the form Gψψ while couplings to a pseudoscalar ﬁeld ¯ 5 ψ.
. The SU(3) symmetry for the quark wavefunctions requires an octet of massless vector boson called gluons to make the LaGrangian gauge invariant. We expect ﬁelds due to currents to change sign but ﬁelds due to static charges to remain unchanged.
2. leaving the charge and energy unchanged.24
Homework Problems
σk 0 0 σk
1. Instead of having 3 sigma matrices to do rotations in the lowest dimension representation of the group. would be of the form iGψγ
35. Prove that Σk = iγ4 γ5 γk where γ5 =
Prove that [γ1 . This operator should reverse both momentum and spin for an electron. Deﬁne: Σk = . SU(3) has eight lambda matrices. Find the “Time Reversal” operator for Dirac spinors.) The Strong interactions are based on the SU(3) group. 5.
2.602 × 10−19 coulomb (SI) h ¯ c = 1973 eV ˚= 197.3 MeV F A a0 =
h ¯ αme c
= 1/137 =
e2 4π 0 hc ¯
1 Fermi = 1..
P (x) =
2 2 √ 1 e−x /2σ 2πσ2
dr r e
n −ar
=
n! an+1
E=
m 2 c4 + p 2 c2
GENERAL WAVE MECHANICS
E = hν = hω ¯ Δp Δx ≥ ψ(x) = pop =
h ¯ 2 ∞ −∞
λ = h/p ΔA ΔB ≥
h dp φ(p) eipx/¯ i 2 [A.602 × 10−12 erg 1 ˚= 1.11 × 10−28 g = 0.3.529 × 10−8 cm
me = 9..511 MeV/c2 gp = 5. Ly ] = i¯ Lz h Aij = ui Auj
ψi = ui ψ
=
+
[H.4...551
36
Formulas
h ¯ = 1.6
∞
= 0.38 × 10−16 erg/◦ K μBohr =
∞ −∞ e¯ h 2me c
c = 3.0 × 10−8 cm A mp = 938.05 × 10−27 erg sec 1eV = 1. t) = uj (x)e−iEj t/¯ dψ dx
xop = i¯ ∂p h∂
−¯ 2 ∂ 2 ψ h 2m ∂x2
Huj (x) = Ej uj (x) ψ(x) continuous Δ dψ dx =
2mλ ψ(a) for h2 ¯ ∞ ∗ −∞
+ V (x)ψ = i¯ ∂ψ h ∂t
continous if V ﬁnite
V (x) = λδ(x − a) ui uj = δij
i
φψ = φ=
i
dxφ (x)ψ(x)
ui ui  = 1 ψ(x) = xψ
∗
ai u i
ai = ui φ
φAψ = φAψ = A† φψ = ψA† φ
1 [ 2m (p
φ(p) = pψ Hψ = Eψ [L2 . x] =
e 2 c A) h ¯ i
+ V (r)]ψ(r) = Eψ(r) [Lx .579 × 10−8 eV/gauss
∞ −∞
dx f (x) δ(g(x)) =
−∞
2
1 dg f (x)  dx  g(x)=0
dx f (x) δ(x − a) = f (a)
∞ n=0 An n!
dx e−ax =
∞ n=1.00 × 1010 cm/sec α=
e2 hc ¯
e = 1.3 MeV/c2 kB = 1.
π a
n−1 θn 2 n! (−1)
use
∂ ∂a
for other forms
∞
n θn 2 n! (−1)
eA =
sin θ =
∞ 0
cos θ =
n=0. B]
p = hk ¯ ΔA = φ(p) = A2 − A
√1 2π¯ h ∞ −∞ 2
√1 2π¯ h
h dx ψ(x) e−ipx/¯
h ∂ ¯ i ∂x
Eop = i¯ ∂t h∂
h ψj (x.5. Lz ] = 0
d A dt ∂A ∂t i h ¯
+
[px .6 MeV/c2 ge = 2 +
α π
= 0. A]
.0 × 10−13 cm mn = 939.
σj ] = 2i ijk σk 0 −i σy = i ⎛ 0 −i √ 0 2 ⎜√ 0 Sy = h ⎝ i2 ¯ 0
i √ 2
−i √ ⎟ 2 ⎠ 0
0
⎞
{σi . σj } = 0 1 0 σz = 0 −1 ⎛ 1 0 Sz = h ⎝ 0 0 ¯ 0 0
⎞ 0 0 ⎠1 −1
HYDROGEN ATOM
H=
p2 2μ
−
Ze2 r ∞
ψn
k −ρ/2
m
= Rn (r)Y
h ¯ αμc
m (θ. φ + π) = (−1) Y
+
Rn (r) + V (r) +
Rn (r) = ERn (r) h
(1)
j0 (kr) =
sin(kr) kr
n0 (kr) = μ=
− cos(kr) kr
(kr) = j (kr) + in (kr)
ge 2mc S
H = H0 − μ · B
¯ Si = h σi 2 0 1 σx = 1 ⎛ 0 0 ⎜√ Sx = h ⎝ 12 ¯ 0
e 2mc L
μ=
1 √ 2
0
1 √ 2
1 √ ⎟ 2 ⎠ 0
0
⎞
[σi . 2.. Lj ] = i¯ h L Y
2 m ijk Lk 2 m
[L2 ..6 eV n2
2r na0
−Zr
n = nr + + 1 Rn (ρ) = ρ
k=0 Z R10 = 2( a0 ) 2 e
4 3
a0 = ak ρ e
−Zr a0
= 0.
9..n−1 ∝ rn−1 e−Zr/na0
p H1 = − 8m3 c2 −e2 gp 3mMp c2 S eB 2mc (Lz
H3 = HB =
· Iδ(r)
m1 m2 m1 +m2 e2 H2 = 2m2 c2 r3 S · L 2g mα4 mc2 ΔE3 = p p n3 (f (f 3M
μ=
3 1 √ ( Z ) 2 ( Zr ) e 2a0 a0 3 2a0 2 2 μc2 Ze2 ψn m  er ψn m = n2 a0 = Zαn2 1 1 3 ΔE12 = − 2n3 α4 mc2 ( j+ 1 − 4n ) 2
+ 1) − I(I + 1) − 3 ) 4 for j = ±
1 2
+ 2Sz )
ΔEB =
e¯ B h 2mc (1
±
1 2 +1 )mj
.3
un (x) = A=(
ak y k e−y
2
/2
ak+2 = A† = ( A n =
k=0 mω 2¯ x h
p + i √2m¯ ω ) h
[A. 1. φ)
eiφ sin θ cos θ
2
Y = ei
∂ ∂r 2
2
sin θ
2 ∂ r ∂r
= (−1)m Y ∗ m
( +1)¯ h 2μr 2
− θ. A† ] = 1 u0 (x) = ( mω ) 4 e−mωx hπ ¯
1 2
A† n =
(n + 1) n + 1
(n) n − 1
/2¯ h
ANGULAR MOMENTUM
[Li .552
HARMONIC OSCILLATOR
H=
p 2m
2
+ 1 mω 2 x2 = hωA† A + 1 ¯ ω ¯ 2 2h
∞
9.m±1 3 4π 5 16π
L± = Lx ± iLy Y00 = Y22 =
−¯ h 2μ
2
( + 1) − m(m ± 1) Y e
iφ
Y11 = − e2iφ sin2 θ Y21 = − Y
(−m)
sin θ
Y10 = Y20 = Y
m (π
cos θ (3 cos2 θ − 1)
m (θ. Li ] = 0 Lz Y L± Y
m m
Y∗ Y m
m
m
dΩ = δ
δmm
= ( + 1)¯ Y h
√1 4π 15 32π φ
= m¯ Y h =h ¯
3 8π 15 8π
− ≤m≤
. φ)
En = − Z
2
α2 μc2 2n2
= − 13.. 1..1
2(k−n) (k+1)(k+2) ak mω 2¯ x h p − i √2m¯ ω ) h
En = (n + 1 )¯ ω 2 h y=
mω h x ¯
n = 0. . n − 1 ρ= e 2a0
−Zr
ak+1 =
k+ +1−n (k+1)(k+2 +2) ak
3
−8μE r h2 ¯
=
Z R20 = 2( 2a0 ) 2 (1 −
Zr 2a0 )
R21 =
Rn.
m+ 1 2 2
= =
+m+1 2 +1 Y m χ+ −m 2 +1 Y m χ+
+
−m 2 +1 Y .mj = ψ ψj.m+ 1 2 2 − 1 .m+1 χ− +m+1 2 +1 Y .m+1 χ−
and any and any
−
PERTURBATION THEORY AND RADIATIVE DECAYS
(1) En
= φn H1 φn
1 i¯ h t 0
En =
(2)
 φk H1 φn 2 (0) (0) k=n En −Ek
cnk =
(1)
φk H1 φn (0) (0) En −Ek
cn (t) =
h dt ei(En −Ei )t /¯ φn V (t )φi
Fermi’s Golden Rule: Γi→f = Γrad = m→k
2π h ¯
3
Γi→f =
2π h  ¯
ψf V ψi 2 ρf (E)
k
Vd ( (2π¯pk ) Mf i 2 δ 3 (momentum conservation) δ(Energy conservation) h )3
α dΩp ωkm  φm e−ik·r · pφk 2 2πm2 c2 α 3 ΓE1 = 2πc2 dΩp ωkm  φm  · rφk 2 m→k − +i +i √ ˆ · r = 4π ( z Y10 + x 2 y Y11 + x√2 y Y1−1 ) ˆ 3 I(ω) ∝ (ω−ω0 Γ/2 Γcollision )2 +(Γ/2)2 2 +1 ∞ 4αω 3 ∗ Γtot = 3c2in 2 +1 Rn Rn r3 dr 0 2 +1 pf dσ 1 ˜ ˜ ( dΩ )BORN = 4π2 h4 pi mf mi V (Δ )2 V (Δ ) = ¯
Δl = ±1. Δs = 0 ·k =0 = Pσ for
3 mkT
( Δω )Dopler = ω = +1 −1 Δ=
pf −pi h ¯
kT mc2
d3 r e−iΔ·r V (r )
ATOMS AND MOLECULES
Hund: 1) max s Erot =
( +1)¯ h 2I
2
2)max ≈
1 2000
(allowed)
1 h 2 )¯ ω
3) min j (≤ ≈
1 50
1 2
shell) else max j
eV
Evib = (n +
eV
. m sms )Y
m
L · S = 1 (J 2 − L2 − S 2 ) 2 χsms =
m ms
=
m ms
jmj s m sms Y for s = for s =
m 1 2 1 2
χsms
ψj.553
ADDITION OF ANGULAR MOMENTUM
J =L+S ψjmj
s
 − s ≤ j ≤ + s C(jmj .mj = ψ
+ 1 .