Molecular Orbitals of Simple Diatomic Molecules

Practical 4

Aim:
Investigating the trends in molecular orbital energies for different diatomic molecules using
Scigress to compute and view the molecular orbitals. Thus, allowing us to understand how
atomic orbitals combine to form molecular orbitals.

Justification of Level of Theory:

As we are calculating energies, the semi empirical AM1 method is the most suitable for this
practical as it includes the valence electrons only. This is essential as it is used within the
calculations, enabling us to compare the energetics of different molecules.

Results

C2 C2 F2 F2
MO Name MO MO Name MO

3σu* 3σu*

1πg* 1πg*

1πg* 1πg*

3σg 1πu

1πu 3σg

1πu 1πu

2σu* 2σu*

2σg 2σg
Molecular Orbitals of Diatomic Molecules 1
Graph of MO energy for different diatomic molecules

MO Energies
10

0
C2 MO Energy (eV) N2 MO Energy (eV) F2 MO Energy (eV)
-10

-20

-30

-40

-50

-60

2σg 2σu* 1πu 1πu

3σg 1πg* 1πg* 3σu*

C2 MO N2 MO F2 MO
MO Name Energy Energy Energy
(eV) (eV) (eV)

2σg -33.307 -41.393 -48.351

2σu* -14.554 -21.43 -44.876
1πu -12.266 -16.192 -17.466
1πu -12.266 -16.192 -17.466
3σg -2.758 -14.323 -19.259
1πg* 1.559 1.003 -14.281
1πg* 1.559 1.003 -14.281
3σu* 5.121 6.031 0.563
Conclusion

C2 is located in the P block therefore, has a substantial interaction between the S and P orbital.
This leads to a flip in the order of the 3σg and 1πu MO. Whereas, F2 is a smaller homo-nuclear
diatomic molecule therefore, the energies of the sigma orbitals drop below that of the pi
orbitals; the σg orbital lies higher in energy than the 1πu orbital due to mixing of the S and P
orbitals. The 3σu* was found to be an anomaly in the F2 MO energy, as it does not follow the
general trend, as it is the only positive value. This is due to the S-P mixing, which pushes the 3σg
orbital above the 1πu* orbital in energy. In turn destabilizing the 3σg and 3σu* orbitals. In F2 the

Molecular Orbitals of Diatomic Molecules 2

HOMO is the 1πg* and the LUMO is the 3σu* whereas, in C2 the HOMO is 1πu and the LUMO is
the 3σg. Moreover, the MO colour change represents the different phases that occur, i.e.
positive or negative. The C2 and F2 molecules illustrate different phases depending on whether
the molecule contains unoccupied orbitals. Partially filled orbitals are due to empty P orbitals,
this is where bonding occurs. If there is a net positive overlap between the orbitals, a bonding
MO results. If there is a net negative overlap, an antibonding MO results thus, atomic orbitals
combine if they have matching symmetries. These AO’s combine more strongly as their
energies approach equally thus, a bonding molecular orbital formed from atomic orbitals of
different energies will have a larger contribution from the lower energy AO. Consequently, the
antibonding MO will have a larger contribution from the higher energy AO.

Molecular Orbitals of Diatomic Molecules 3