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Chapter 7: Quantum Theory: Introduction and Principles

THE ORIGINS OF QUANTUM MECHANICS electromagnetic field. a field that acts on moving charged particles.Chapter 7: Quantum Theory: Introduction and Principles classical mechanics. an oscillating electric and magnetic disturbance that spreads as a harmonic wave through space. electric field. . the laws of motion introduced in the twentieth century by Heisenberg and Schrödinger. the laws of motion introduced in the seventeenth century by Isaac Newton. a field that acts on charged particles. magnetic field. quantum mechanics.

frequency. the reciprocal of the wavelength. the peak-to-peak distance of a wave. the number of times per second that a displacement returns to its initial value. an object capable of emitting and absorbing all frequencies of radiation uniformly. 7. v electromagnetic spectrum. wavenumber. ɶ . the range of frequencies exhibited by the electromagnetic field and its classification into regions.Chapter 7: Quantum Theory: Introduction and Principles wavelength. .1 The failures of classical physics black body. v. λ.

Planck’s constant. dE = ρdλ. ultraviolet catastrophe.1 The failures of classical physics (cont…) Rayleigh–Jeans law. h = 6. ρ . quantization of energy. the divergence of the energy density of black-body radiation at high frequencies. ρ = 8πkT/λ 4. the proportionality constant between the range of wavelengths and the energy density in that range: dE = ρdλ. . the limitation of energies to discrete values. density of states.626 08 × 10–34 J s.Chapter 7: Quantum Theory: Introduction and Principles 7.

. dE = ρdλ. CV. ρ = (8πhc/λ5)/(ehc/λkT – 1).) Planck distribution.1 The failures of classical physics (cont. CV. and close to 25 J K–1 mol–1. Dulong and Petit’s law: the molar heat capacities of all monatomic solids are the same. T Debye formula.m = 3Rf. f = (θE/T)2{eθ_E/2T/(eθ_E/T – 1)} Einstein temperature.m = 3Rf.Chapter 7: Quantum Theory: Introduction and Principles 7. Einstein formula. f = 3 θD 3 ∫ θD / T x 4e x 0 (e x −1 ) 2 dx . θE = hv/k..

the relation between the change in energy and the frequency of the radiation emitted or absorbed: ∆E = hv. spectrum.1 The failures of classical physics (cont.Chapter 7: Quantum Theory: Introduction and Principles 7. spectroscopy. the detection and analysis of a spectrum. spectroscopic transition. absorbed. a change of state that gives rise to a feature in spectrum. . the record of intensity of light transmitted. or scattered as a function of frequency. Bohr frequency transition.. wavelength.) Debye temperature. or wavenumber. θD = hvD/k.

photoelectric effect. work function. the diffraction of electrons by a crystal. . Φ. a particle of electromagnetic radiation. electron diffraction. wave–particle duality. Davisson–Germer experiment. the diffraction of electrons by an object in their path.2 Wave–particle duality photon. the joint particle and wave character of matter and radiation.Chapter 7: Quantum Theory: Introduction and Principles 7. the ejection of electrons from metals when they are exposed to ultraviolet radiation: ½mev2 = hv – Φ. de Broglie relation. λ = h/p. the energy required to remove an electron from the metal to infinity .

3 The Schrödinger equation time-independent Schrödinger equation. ψ .Chapter 7: Quantum Theory: Introduction and Principles THE DYNAMICS OF MICROSCOPIC SYSTEMS wavefunction. a mathematical function obtained by solving the Schrödinger equation and which contains all the dynamical information about a system. –( ħ2/2m)(d2ψ/dx2) + V( x) ψ = Eψ. the value of |ψ|2 at a point is proportional to the probability of finding the particle at that point. 7.4 The Born interpretation of the wavefunction Born interpretation. 7. .

The volume element in spherical coordinates is r2sin θ drdθdφ. normalization constant.Chapter 7: Quantum Theory: Introduction and Principles 7.) Born interpretation. probability density. the square-root of the probability density (the wavefunction itself).4 The Born interpretation of the wavefunction (cont. the colatitude θ. . and the azimuth φ. spherical polar coordinates. confinement of a dynamical observable to discrete values. the radius r . N = 1/{∫ψ*ψ dx}1/2. probability amplitude. the probability of finding a particle in a region divided by the volume of the region.. quantization. the value of |ψ|2 at a point is proportional to the probability of finding the particle at that point.

.) constraints on the wavefunction. the operator for the total energy of a ˆ ψ = Eψ . system. and be square-integrable). H .Chapter 7: Quantum Theory: Introduction and Principles 7.4 The Born interpretation of the wavefunction (cont. a point where a wavefunction passes through zero . have a continuous first derivative.5 The information in a wavefunction node. QUANTUM MECHANICAL PRINCIPLES 7. be single-valued. something that carries out a mathematical operation on a function. operator. the conditions a wavefunction must obey (be continuous. hamiltonian operator.

5 The information in a wavefunction (cont.Chapter 7: Quantum Theory: Introduction and Principles 7. eigenfunction.. x ˆ = x ×. momentum operator. an operator for which it is true that ∗ ∗ ˆ ∗ ˆ ψ Ωψ dx = ψ Ωψ dx ∫ i j {∫ j i } . eigenvalue. hermitian operator. measurable properties of a system.) ˆ ψ = ωψ . position operator. an equation of the form Ω observable. the constant ω in the eigenvalue equation Ω ˆ ψ = ωψ . p ˆ x = (ħ/i)d/dx. the function ψ in the eigenvalue equation Ω ˆ ψ = ωψ . eigenvalue equation.

a linear combination of wavefunctions. with arbitrary precision.Chapter 7: Quantum Theory: Introduction and Principles 7.5 The information in a wavefunction (cont. 2 . superposition. ∆p∆q ≥ ℏ . ∫ψi*ψ j dτ = 0.) orthogonal functions.6 The uncertainty principle Heisenberg uncertainty principle: it is impossible to specify simultaneously.. ˆ ψdτ . both the 1 momentum and the position of a particle. complete set of functions. linear combination of two functions. Ω = ∫ψ ∗Ω 7. c1f + c2g. expectation value. functions that can be used to express any arbitrary function as a linear combination.

Ω 2 2 [ ] .6 The uncertainty principle (cont. complementary observables. operators for which Ω ˆ 1. a localized wavefunction formed by superimposing a series of wavefunctions. observables corresponding to non-commuting operators. Ω [ ] [ ] general form of the Heisenberg uncertainty principle: 1 ˆ ˆ ∆Ω 1∆Ω 2 ≥ Ω1 .Chapter 7: Quantum Theory: Introduction and Principles 7.) wave packet. commuting operators. Ω ˆ 2 = 0. Ω ˆ2 =Ω ˆ 1Ω ˆ 2 −Ω ˆ 2Ω ˆ1 commutator. ˆ 1..

5095 × 10 3 J/mol = 1 hartree .5095kc al/mol = 4.Atomic Units SI atomic unit ℏ= mass of an electron : charge : h →1 2π m e = 9.602176 ×10 -19 C ) → 1 4πε 0 ℏ 2 -11 length : Bohr radius a 0 = = 5 .184 × 627.10938 ×10 -31 kg → 1 e (1.21eV = 627. 29177 × 10 m →1 2 me e vacuum permittivi ty ε 0 : 4πε 0 → 1 energy : 27.

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