Theoretical Chemistry HW6

Answer as completely as possible. Show your work.

1. True or false? If false, briefly explain why.

a. No classical analog of the exchange operator exists.

b. An orbital rotation of the occupied canonical Hartree-Fock orbitals yields new

orbitals with the same ground state energy.

c. At all points on the potential energy surface of a molecule, -<V> = 2<T>.

d. Given a two-electron operator Ô2 , D Ô2 D¢ = 0 if D and D’ differ by two or

more spin-orbitals.

e. The pseudoeigenvalue equations Fa Ca = SCae a ;F b C b = SCbe b can be solved

independently.

f. There is no single, unique method to determine partial charges on atoms in

molecules.

2. Is the following two electron spatial function symmetric or antisymmetric with exchange
of the electrons? What spin function(s) is/are associated with this spatial function? What
is the multiplicity of a state with this spatial function?
F = 1
2
[y1s (1)y2s (2) - y2s (1)y1s (2)]
3. Find the terms that arise from a ()2(1)1(2)1 configuration. Which term is expected to
be the lowest in energy?

4. What is the MS value associated with the following function? (Show work for full credit)
1
2
[y1 (1)y2 (2) + y2 (1)y1 (2)] 12 éëa (1) b ( 2) - b (1) a ( 2)ùû
5. Describe the Born-Oppenheimer Approximation and show how the Hamiltonian reduces
with this approximation.

6. What are the advantages of Slater basis functions over Gaussian functions? What are the
advantages of Gaussians over Slaters?

7. What is a polarization function? Why is it useful to include polarization functions in

calculations? What is a diffuse function? What are diffuse functions good at
representing?
8. The restricted Hartree Fock STO-3G orbital energies (in a.u.) for an optimized water
molecule are:
e1: -20.2516
e2: -1.2575
e3: -0.5939
e4: -0.4597
e5: -0.3926
e6: 0.5818
e7: 0.6927
Water has five occupied orbitals and ten electrons. Estimate the ionization potential,
electron affinity and first excitation energy for water using Koopman’s Theorem. What
is one approximation that Koopman’s Theorem makes?

9. Why do the Hartree-Fock equations need to be solved iteratively?

10. Explain what spin-orbit coupling is and briefly discuss the difference between Russell-
Saunders coupling and j-j coupling.

1 N N
11. Convert åå( ab ab - ab ba
2 a b
) from spin orbitals to spatial orbitals.

N N
1
12. Simplify the following integral: c k c l c m c n åå r c k c l c m c p The bra and ket
i=1 j>i ij

represent Slater determinants. Show your work.