Assignment-2

1. Which of the following expressions correctly represents the spin-integrated anti-

symmetrized two-electron integral in the Hartree-Fock energy?

1 N /2  1 1 
a)   2 i j
4 i, j 
i j − i j i j 
r12 r12 

1 N /2  1 1 
b)   2 i j
4 i, j 
i j + i j i j 
r12 r12 

1 N /2  1 1 
c)   4 i j
2 i, j 
i j + 2 i j  ji 
r12 r12 

1 N /2  1 1 
d)   4 i j
2 i, j 
i j − 2 i j  ji 
r12 r12 

Ans: d)

2. In linear variation method using two orthogonal basis functions, the two roots
obtained are  0 and  1 (  0   1 ) . The correct relation of these roots with exact

ground and first excited state energies, E0 and E1 , respectively, is

a)  0  E0 and  1  E1

b)  0  E0 and  1  E1

c)  0  E0 and  1  E1

d)  0  E0 and  1  E1

Ans: d)

3. What does the term “configuration” refer to in Configuration Interaction?

a) A specific arrangement of atoms in a molecule.
b) A set of molecular orbitals.
c) Slater determinants generated by distributing electrons among orbitals.
d) The spatial arrangement of electrons within an atomic orbital.
Ans: c)

4. Which expression correctly represents the antisymmetrization of a two-electron wave

function using spin-orbitals 1 and  2 ? (Here, r1 and r2 are space-spin coordinates)

a)  ( r1 , r2 ) = 1 ( r1 )  2 ( r2 ) −  2 ( r1 ) 1 ( r2 )

b)  ( r1 , r2 ) = 1 ( r1 ) 1 ( r2 ) +  2 ( r1 )  2 ( r2 )

c)  ( r1 , r2 ) = 1 ( r1 )  2 ( r2 ) +  2 ( r1 ) 1 ( r2 )

d)  ( r1 , r2 ) = 1 ( r1 )  2 ( r1 ) −  2 ( r2 ) 1 ( r2 )

Ans: a)

5. The linear variational method becomes exact when:

a) the basis set is small and localized.
b) the basis set is complete and all the configurations are included.
c) the trial wavefunction is a Slater determinant.
d) the potential energy is neglected.

Ans: b)

6. Two trial wavefunctions 1 = c1 x(a − x) and 2 = c1 x(a − x) + c2 x 2 (a − x)2 give

approximate ground state energies E1 and E2 , respectively, ( E2  E1 ) for the

microscopic particle in 1-D box by using the variation method. If the exact ground
state energy is E0 , the correct relationship between E0 , E1 and E2 is:

a) E0 = E1 = E2 b) E0  E1  E2

c) E0  E2  E1 d) E0  E2 = E1

Ans: c)
 7. How is the Hartree-Fock energy expressed in terms of one-electron and two-electron
integrals? (Here, i and j are spin orbitals)

 ( 2 J ij + Kij )
1
a) EHF =  hii +
i 2 i, j

 ( 2 J ij − Kij )
1
b) EHF =  hii −
i 2 i, j

 ( 2 J ij + Kij )
1
c) EHF =  hii −
i 2 i, j

 ( J ij − Kij )
1
d) EHF =  hii +
i 2 i, j

Ans: d)

8. In the Lagrange variational method, the Lagrangian L is defined as: (When,  is a

trial wavefunction and  is any other arbitrary function)
 Hˆ 
a) L    = +  (   − 1)
 

 Hˆ 
b) L    = +  (   − 1)
 

 Hˆ 
c) L    = +  (   + 1)
 

 Hˆ 
d) L    = +  (   + 1)
 

Ans: b)

9. The Rayleigh-Ritz variational principle provides an upper bound to the ground state
energy. Which of the following expressions correctly represents this principle? (When,
 is a trial wavefunction and  is any other arbitrary function)
 Ĥ 
a) Evar 
 
  Ĥ 
b) Evar 
 

 Ĥ 
c) Evar 
 

 Ĥ 
d) Evar 


Ans: a)

10. Which one of the following is the correct mathematical formula for the Coulomb term
(J) in the Hartree-Fock energy expression? (Here, i and j are spin orbitals)
1
a) 
i j
 i (1)  j ( 2 )
r12
 j (1)  i ( 2 )

1 1
b) 
2 i j
 i (1)  j ( 2 )
r12
 i (1)  j ( 2 )

1
c) 
i j
 i (1)  j ( 2 )
r12
 i (1)  j ( 2 )

d) Both b) and c)

Ans: d)