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 ji
r12 r12
1 N /2 1 1
d) 4 i j
2 i, j
i j − 2 i j ji
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)
