Quantum Chemistry II – Electronic Spectroscopy

Abhinav Senthil
13.1 Why can it be unclear whether a material is a semiconductor or an insulator?

Both insulators and semiconductors share the property that there is a clear band gap
between successive bands. That is to say that there is a meaningful energy difference
between the highest occupied band and the lowest unoccupied band. In general, if the
energy gap Egap >> kBT, for T below the melting point, we can consider it to be an insulator.
At sufficiently high temperature such that E ≈ kBT, from the Boltzmann distribution we can
easily predict that electrons will be able to overcome the relatively small energy difference
between the HOMO and LUMO. Consequently, at lower temperatures, both semiconductors
and insulators will behave quite similarly.
13.6 What evidence can you find in Table 13.1 that C-C sp bonds are stronger than sp3 bonds
In table 13.1 we can see the bond hybridisation compared with the C-C bond length. We can see that
with increasing s character and decreasing p character, the bond length is decreasing. Bond length is
inversely proportional to bond strength, so we can see evidence that sp hybridised C-C bonds are
stronger than sp3 hybridised C-C bonds.

13.11 In using the sum of the occupied MO energies to predict the bond angle in H2A molecules,
the total energy of the molecule is assumed to be proportional to the sum of the occupied MO
energies. This assumption can be justified. Do you expect this sum to be greater than or smaller
than the total energy?

In general, the sum of MO energies should be greater than the total energy of the molecule, as
energy is released during the bond formation process which helps stabilise the molecule in its lowest
energy state.

13.1 Show that the determinantal property used in the discussion of localized and delocalized
orbitals in Section 13.6 is correct

For the simple 2x2 we have D = ad – bc. For the expanded matrix, we have D = a(γb + d) – b(γa + c) =
(aγb + ad) – (aγb + bc). We can see the aγb terms cancel to give D = ad – bc which shows that the
determinant is retained when we apply this function on the basic 2x2 matrix.

13.2 Predict whether LiH2+ and NH2- should be linear or bent based on the Walsh correlation
diagram in Figure 13.11. Explain your answers.

For the LiH2+ molecule, the 1a1 orbital is occupied by the 2 valence electrons. From the
Walsh diagram, we can determine the molecule should have a bent structure as the orbital
energy of 1a1 increases with bond angle.
NH2- has the same electron configuration as H 2O with 8 valence electrons. The orbitals that
are filled are then similar to those of water, which would imply that overall orbital energy
can be minimized with a similar bond angle. NH2- should also be bent for that reason.
13.8 Show that the water hybrid bonding orbitals given by ψ a = 0.55φ2pz + 0.71φ2px – 0.45φ2s and
ψb = 0.55φ2pz - 0.71φ2px – 0.45φ2s are orthogonal

We have 0.552 – 0.712 + 0.452 = 9*10-4 ≈ 0, showing that ψa and ψb are orthogonal.

13.9 Predict which of the bent molecules, BH 2 or NH2, should have the larger bond angle on the
basis of the Walsh correlation diagram in Figure 13.11. Explain your answer.

The BH2 molecule has 5 valence electrons compared to the 7 valence electrons of the NH 2 molecule.
We know that NH2 has quite a small angle of around 103 degrees as we have electrons in
orbitals all the way up to 1b1, sum of orbital energies to minimize the total energy is lowest
at a low bond angle. As BH 2 has only 5 valence electrons, electrons only occupy up to 2a 1.
We no longer have to minimize the energy of the 1b 1 orbital as it is unoccupied. That energy
of the 1b1 orbital from the Walsh diagram is proportional to bond angle, so the angle of BH 2
is likely to be greater than that of NH 2 as we no longer have to consider the energy
contribution of the 1b1 orbital.
13.16 The occupied MOs of ammonia are shown next along with the MO energies. Indicate which
AOs are most important in each MO and indicate the relative phases of the AOs. Classify the MOs
as localized or delocalized, and bonding, nonbonding or antibonding

The MO corresponding to -423 eV represents a nonbonding orbital that is localised. The MO

corresponding to -31.0 eV represents the in-phase overlap between the 2s orbital of N and the 1s
orbital of H. It is bonding and delocalised. The two MOs corresponding to -17.1 eV represent the
different orientations, they are both delocalised, in phase and bonding. The MO corresponding to -
11.4 eV is in-phase, delocalised and nonbonding.

13.21 Determine the AO coefficients for the lowest energy Hückel π MO for butadiene

1,3-Butadiene has 4 conjugated p orbitals, so we consider ψ π = c1φ2pz1 + c2φ2pz2 + c3φ2pz3 + c4φ2pz4

We can then construct a 4x4 Hückel matrix with the element 1 on element H ij for all ij such that
there exists a bond between the i th and jth carbon.

( ) ( )
0 1 0 0 1.62 0 0 0
1 0 1 0 0 0.62 0 0
We then diagonalise to obtain E = Then we can
0 1 0 1 0 0 −0.62 0
0 0 1 0 0 0 0 −1.62

( )
α +1.62 β 0 0 0
0 α + 0.62 β 0 0
substitute with α and β to find E =
0 0 α−0.62 β 0
0 0 0 α−1.62 β

We then have ε1 = α + 1.62β, ε2 = α + 0.62β, ε3 = α – 0.62β and ε4 = α - 1.62β. We have the

lowest energy MO: ε1 = α + 1.62β as β is negative. We can also use the matrix with α – ε on
the principal diagonal and β for elements with bonds between carbons.

( )
α–ε β 0 0
β α–ε β 0
As we have ε = α + 1.62β, we can substitute for ε and construct
0 β α–ε β
0 0 β α –ε
the equations -1.62βc1 + βc2 = 0. We find c2 = 1.62c1. From the second row we have βc 1 -
1.62βc2 + βc3 = 0. Substitute for c2 to find c1 – 2.62c1 + c3 = 0, thus c3 = 1.62c1 and we find c2 =
c3. Similarly, from row 4 we can find βc 3 – 1.62βc4 = 0 we can find c3 = 1.62c4 and thus c4 = c1.
Finally, from the normalisation condition, we have c 12 + 1.62c12 + 1.62c12 + c12 = 1. Therefore,
2c12 + 5.2488c12 = 1 and c1 = 0.372
If c1 = 0.37, then c2 and c3 = 0.602 and c4 = 0.372
Finally for the lowest energy MO for butadiene, we have ψ1 = 0.372φ2pz1 + 0.602φ2pz2 +
0.602φ2pz3 + 0.372φ2pz4