Scribd
Upload
16 views4 pages

Assignment 3

The document contains 10 multiple choice questions about concepts in quantum chemistry and the Hartree-Fock method. Key concepts covered include the exchange operator K, Slater determinants, Lagrange multipliers, virtual and occupied orbitals, and the Fock operator.

Uploaded by

Vemuri Lakshmi ganesh
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
16 views4 pages

Assignment 3

The document contains 10 multiple choice questions about concepts in quantum chemistry and the Hartree-Fock method. Key concepts covered include the exchange operator K, Slater determinants, Lagrange multipliers, virtual and occupied orbitals, and the Fock operator.

Uploaded by

Vemuri Lakshmi ganesh
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 4

Assignment-3

1. What role does the exchange operator (K) play in the Hartree-Fock method?
a) It corrects for basis set incompleteness.
b) It introduces correlation effects.
c) It accounts for relativistic effects.
d) It minimizes the total energy.
e) It models the exchange of electrons between spatial orbitals.

Ans: e)

2. The expectation value for a determinant is given as:


 Ĥ  = h11 + h22 + h33 + J12 − K12 + J13 − K13 + J 23 − K 23 What would be the

corresponding determinant?

a) c)

b) d)

e) f)

Ans: c)

3. If the Lagrangian for energy minimization is given as:


N
1 N
L= i h i +  i  j i  j −  ij   i  j −  ij  . Which of the following
i =1 2 i, j i, j

expressions correctly represents the variation of the Lagrangian with respect to the
Lagrange multiplier kl ?
L
a) =  k  l −  kl
kl

L
b) =  ( 2 Eij − 1)
kl ij

L
c) =  ( 2 H ij − 1)
kl ij

L
d) =  ( 2 Sij − 1)
kl ij

L
e) = 2 ( 2Cij − 1)
kl ij

Ans: a)

4. For a Slater determinant of Carbon atom in Hartree-Fock theory, which of the


following expressions accurately represents the one-electron term in the Hartree-Fock
energy? (Here, i and j are spin-orbitals in the Slater determinant)
a) h
ij
ij

b)  2h
i
ij

c) h
i
ii

1
d)  hii
2 i
1
e)  hij
2 ij

Ans: c)

5. What is the expression for the electron affinity (EA) in terms of orbital energies in
Koopmans’ theorem?
a) LUMO −HOMO

b) HOMO −LUMO

c) − HOMO
d) LUMO

e) − LUMO

Ans: e)

6. In the Lagrange variational minimization of Hartree-Fock energy, what happens to the


Lagrange multiplier λ during the iterative process?
a) It remains constant.
b) It increases monotonically.
c) It decreases monotonically.
d) It adjusts to minimize the energy at each iteration.
e) It oscillates.

Ans: d)

7. Consider a given open-shell determinant for Boron atom in Hartree-Fock theory.


What is the correct expression for the expectation value of the energy in terms of one-
electron Hamiltonian and two-electron coulomb (J) and exchange (K)
terms?
a)  Hˆ  = 2h11 + 2h22 + 2h33 + 4 J12 − 2 K12 + 2 J13 − K13 + 2 J 23 − K 23

b)  Hˆ  = 2h11 + 2h22 + h33 + 2 J12 − 2K12 + 2 J13 − K13 + 2 J 23 − K 23

c)  Hˆ  = 2h11 + 2h22 + h33 + 4 J12 + 2K12 + 2 J13 − K13 + 2 J 23 − K 23

d)  Hˆ  = 2h11 + 2h22 + 2h33 + 4 J12 − K12 + 2 J13 − K13 + 2 J 23 − K 23

e)  Hˆ  = 2h11 + 2h22 + h33 + 4 J12 − 2K12 + 2 J13 − K13 + 2 J 23 − K 23

Ans: e)

8. Which of the following is a characteristic of "virtual orbitals"?


a) They have negative orbital energies.
b) They have zero electron density.
c) They are unoccupied in the ground state.
d) They are always doubly occupied.
e) They are degenerate.

Ans: c)

9. What does the constraint Sij − I = 0 represent in a Lagrange function for Hartree-Fock

energy minimization?
a) Constraint on the nuclear repulsion.
b) Orthogonality constraint for the orbitals.
c) Requirement for electron-electron repulsion minimization.
d) Constraint on the kinetic energy.
e) Orbital coefficient adjustment.

Ans: b)

10. What is the expression for Fock operator in the Canonical Hartree-Fock equation?
 1 
a) f (1) = h(1) +    j (2)  − P12  j (2) 2
j  r12 
1
b) f (1) = h(1) +    j (2) (1 − P12 ) i (2) 2
j r12

P 
c) f (1) = h(1) +    j (2)  12 − 1 j (2) 2
j  r12 
1
d) f (1) = h(1) +    j (2) (1 − P12 ) j (2) 2
j r12

1
e) f (1) = h(1) +    i (2) (1 − P12 ) j (2) 2
j r12

Ans: d)

You might also like