Assigned problems for Lectures 25-27 Molecular Orbital Theory and

Homonuclear Diatomic Molecules

1. Give the groundstate electron configuration for

(a)H-2 , (b)N 2 , (c)O2
What are the bond orders (bo)

answer
( a) : H-2 (3 electrons) : 1σ 2 2σ * bo = 0.5
(b) : N 2 (10 electrons) : 1σ 2 2σ *2 1π 4 3σ 2 bo = 3
(c) : O2 (12 electrons) : 1σ 2 2σ *2 1π 4 3σ 2 2π *2 bo = 2

2. From the groundstate electron configuration of B2 and C2

predict which molecule
should have the greater dissociation energy
Answer :

B2 (6 electrons) : 1σ 2 2σ *2 1π 2 b =1

C2 (8 electrons) : 1σ 2 2σ *2 1π 4 b=2

The bond orders of B2 and C2 are respectively 1 and 2; so

C2 should have the
greater bond dissociation enthalpy. the experimental values are
approximately 4eV and 6eV respectively.

3. Consider a bonding electron in a diatomic molecule from the

molecular orbital point of view. If the probabilities of finding
the electron in atomic orbitals ψ A and ψ B are 0.25 and 0.75,
respectively, what is the LCAOwavefunction for the electron
(Neglect overlap)
Answer :
Since the electron moves only in orbitals ψ A and ψ B we must have
Ψ = C1ψ A + C2 ψ B . The square of the coefficients equals the corresponding
probability since ψ A and ψ B are orthonormal

1 1
= ∫ C1ψ A C1ψ A dv =C12 ∴ c1 = ±
4 2

3 3
likewise = C2 2 ∴ C2 = ±
4 2
The overall probability must be equal to 1

C12 + C2 2 = 1

Thus there are two possible wave functions

1 3
Ψ± = ψA ± ψB
2 2
1
The Ψ+ is the bonding combination. The choice of c1 = − results
2
in two more wavefunctions which are just negatives of the
first two , and so describe the same physical states

4. The term symbol for the groundstate of the N+2 ion is 2 Σ g .

What is the total spin angular momentum of the molecule?
Show that the term symbol agreres with the electron configuration
that would be predicted by using the build - up principle.

answer :
The left superscript is the value of 2S + 1, so 2S + 1 = 2 implies that
1
S = . The symbol Σ indicates that the orbital angular momentum
2
around the molecular axis is zero. The latter implies
that the unpaired electron must be in a σ - orbital. From the
orbital level diagram for homonuclear diatomic molecules in the text
we predict the configuration N2 + (9 electrons) :1σ 2 2σ *2 1π 4 3σ1 bo = 2.5,
which is in accord with the 2 Σ g term symbol since 3σ is an even
function and all lower energy orbitals are filled, leaving one unpaired
1
electron, thus S = .
2
 5. One of the excited states of the C2 molecule has the valence
electron configuration 1σ g 2 2σ u *2 1π u1 2π g1. Give the multiplicity
and parity of the term.

Answer
According to Hunds rule, we expect one 1π u electron and one 2π g
electron to be unpaired. hence S = 1 and the multiplicity of the
spectroscopic term is 3. the overall parity is uxg = u since (apart
from the complete core), one electron occupies a u orbital and
another a g orbital.

6. The energy of H+2 with internuclear separation R is given by the

expression
J+K e2
E+ = EH − +
1 + S 4 πε o R
where E H is the energy of an isolated H atom, J is the attractive potential
energy between the electron centered on one nucleus and the charge of
the other nucleus, K is the attraction between the overlap density and one of the
nuclei, and S is the overlap integral. The values are given below. Plot the
molecular potential energy curve and find the bond dissociation energy (in eV)
and the equilibrium bond length

R/a o 0 1 2 3 4

e2
( )
4 πε o R
∞ 1.000 0.500 0.3333 0.255
RH

J / RH 1.0000 0.729 0.473 0.330 0.250

K / RH 1.0000 0.736 0.406 0.199 0.092

S 1.0000 0.858 0.587 0.349 0.189

where R H = 27.3 eV, a o = 52.9 pm , and E H = - 1/2R H

For an answer check with the graph in the text

 7. The same data as in problem 6 may be used to calculate the molecular potential
energy curve for the antibonding orbital , which is given by

J-K e2
E- = E H - +
1 - S 4πε o R
For answer check with graph in text

8. One of the excited states of H2 is 3Πu , and can be considered to be

formed from one H atom in its groundstate and the other in the excited state.
Give the electron configuration of the molecule.

Answer :
Since the molecule has one unit of angular momentum around the axis, and
since one electron is in a σ orbital , the other electron must be in a π orbital.
This suggests that the configuration is 1σ g11π u1 which is consistent
with the designation 3Π u .

9. Normalize the molecular orbital Ψ(1) = ψ A (1) + λψ B (1) in terms of the

parameter λ and the overelap S. Here assume ∫ ψ *A (1)ψ A (1)dv = 1,
∫ ψ B (1)ψ B (1)dv = 1, ∫ ψ A (1)ψ B (1)dv = S
* *

Answer :

∫ Ψ(1) Ψ(1) = N ∫ (ψ A (1) + λψ B (1)) (ψ A (1) + λψ B (1))dv = 1

* 2 *

= N 2 ∫ (ψ *A (1)ψ A (1)dv + N 2 λ2 ∫ (ψ *B (1)ψ B (1)dv + 2λN 2 ∫ (ψ *B (1)ψ A (1)dv

= N 2 (1 + λ2 + 2 Sλ )
1
hence N =
1 + λ2 + 2 Sλ

10. use the date in 6 and 7 to show that the antibonding orbital (E- ) is more anti -
bonding (destabilized compared to a free hydrogen atom) than the bonding
orbital is bonding (stabilized compared to free hydrogen atom)
Answer : We need to determine if E- + E+ > 2E H

J-K e2 J+K e2
E− + E+ = E H - + + EH − +
1 - S 4πε o R 1 + S 4πε o R
e2 [( J − K )(1 + S ) + (1 − S )( J + K )
= 2EH + 2 −
4πε o R (1 − S )(1 + S )

2( SV2 − V1 ) e2
= + 2 E H + 2
1 − S2 4πε o R

2( SV2 − V1 ) e2
Use the data in 6 to show that + 2 >0
1 − S2 4πε o R