You are on page 1of 2

Physics 421 Homework Assignment # 2 Due Wednesday April 17

Spring 2013

1. Pauli Spin Operator The electron spin operator s can be written in matrix form in terms of the Paul spin operator σ = 2s where ( ) ( ) ( ) 0 1 0 −i 1 0 σx = ; σy = ; σz = . 1 0 i 0 0 −1 1 0 Define = and χ− = . 0 1 (a) Verify that these functions are eigenfunctions of s2 and sz , and find the eigenvalues. (b) Show that not only does s satisfy the commutation relations for angular momentum but also 2 = σ 2 = σ 2 = 1 and σ σ + σ σ = 0 (and cyclically). σx x y y x y z (c) Verify the relation (σ · F)(σ · G) = F · G + iσ · F × G χ+ where F and G are any two vector operators which commute with σ . 1 2 (s · r)2 = 4 r . 2. Text (3.2) Direct and exchange integrals for an arbitrary system 3. Ground state energy of the helium atom. ∫ ∞ ∫ ∞ exp (−α(r1 +r2 )) π2 ). dr ⃗1 dr ⃗2 = 20 (The following relation may be helpful for this problem: −∞ −∞ r12 α5 If we neglect interactions between electrons, the ground state energy of the helium atom is 2 4πϵ 0 E = 2Z 2 (− e / 2a0 ) = −108.848eV. The true (measured) value is -79.006 eV.
4πϵ0 > supposing both electrons are in the 1S state. (a) Calculate the interaction energy < e / r12 What is the ground state energy? (b) The value obtained in (a) is a big improvement, but still several eV off. We can easily get a better value by using a variational method, which uses the charge Z ′ of the nucleus as a free parameter. Use ψ = φ(⃗ r1 )φ(⃗ r2 ) where φ is the 1S wavefunction
2

(

)

(

)

Hence show that

1 Z′ 3 Z′ φ(⃗ r) = √ ( ) 2 exp[−( )r] π a0 a0 as a suggested ground state and express the expectation value of the ground state energy in terms of Z ′ . Provide the physical interpretation of the free parameter Z ′ . (c) Calculate Z ′ that minimizes the energy. What is the improved ground state energy? (We suppose that the spin wavefunction is anti-symmetric.) As long as we use wavefunctions in the form of ψ = φ(⃗ r1 )φ(⃗ r2 ) (one-electron approximation), we cannot reduce discrepancies to less than 1 eV. However, introducing correlations into wavefunctions greatly improve the solutions. For example, minimizing the energy using ψ ∼ e−c1 (r1 +r2 ) (1 + c2 r12 + c3 (r1 − r2 )2 ) gives you a minimum energy only 0.035 eV off from the measured value! 1

Text (3.6) Calculation of integrals for the 1s2p configuration 5.7) Expansion of 1/r12 2 . (Optional Problem) Text (3.4.