Molecular Orbitals and Wave Properties of

Electrons
• atomic orbitals can combine constructively to
form a bonding molecular orbital. In the
simplest case two H atoms are joined using a
bonding molecular orbital. The H2 molecule
has lower potential energy (or, is more stable)
than the two isolated H atoms. “Destructive”
combinations of atomic orbitals are also
possible.
 Molecular Orbital Theory
• Atomic orbitals are isolated on atoms.
• Molecular orbitals span two or more
atoms.
• LCAO
– Linear combination of atomic orbitals.

Ψ1 = φ1 + φ2 Ψ2 = φ 1 - φ 2
Electron Density in Bonding and Antibonding
Orbitals
• Bonding orbitals – considerable electron
density between the bonded atoms.
• Non-bonding orbitals – very little electron
density between the bonded atoms
(energetically unfavourable result).
• Bonding and antibonding sigma orbitals are
represented on the next slide.
 FIGURE 11-20

Formation of bonding and antibonding orbitals

 FIGURE 11-21

The interaction of two hydrogen atoms according to molecular theory

 Basic Ideas Concerning MOs
1. Number of MOs = Number of AOs.
2. Bonding (lower energy) and antibonding (higher
energy) MOs formed from AOs.
3. e- fill the lowest energy MO first (aufbau process)
4. Maximum 2 e- per orbital (Pauli Exclusion
Principle)
5. Degenerate orbitals fill singly before they pair up
(Hund’s Rule).
Molecular Orbitals – Learning Objectives

• 1. Construct molecular orbital diagrams for

diatomic molecules composed of elements from
the first period elements (H and He) and the
second period elements (Li, Be, B, C, N, O F
and Ne). This includes species with +ve and
-ve charges. (Eg. O2+ and CN-).
• 2. Label MOs in the MO diagram and show
their relative energies. Indicate whether MOs
are bonding or anti-bonding.
Molecular Orbitals – Learning Objectives

• 3. Use the molecular formula (for neutral

molecules and diatomic ions) and charge to
determine the total number of electrons that
we must accommodate using the MO picture.
• 4. Distribute all of the electrons among the
available MOs – starting with the lowest
energy MOs (sound familiar?).
Molecular Orbitals – Learning Objectives

• 5. After counting the number of electrons in

both bonding and anti-bonding orbitals
determine the bond order.
• 6. Use the MO diagram (and the number of
electrons in the various molecular orbitals) to
determine whether a molecule is diamagnetic
or paramagnetic.
Molecular Orbitals – Learning Objectives

• 7. Understand a surprising feature of

molecular orbital theory. We can accommodate
all of the valence electrons in various
molecular orbitals for a diatomic species and
end up with a bond order of zero!
 Bond Order
• Stable species have more electrons in
bonding orbitals than antibonding.

No. e- in bonding MOs - No. e- in antibonding MOs

Bond Order =
2
 Molecular Orbitals – Nomenclature:

• For the simplest atoms (H, He, Li, Be) only 1s

and 2s orbitals are occupied in the ground
electronic state. The overlap of two 1s orbitals
can only produce a sigma (σ) bond. In the H2
molecule, for example, two 1s atomic orbitals
can combine to form a σ1s bonding molecular
orbital and a σ1s* anti-bonding molecular
orbital. When 2p orbitals come into play we
can form both σ and π molecular orbitals.
 Simplest Diatomics – MO Diagrams

• MO diagrams are initially a bit confusing

because they represent the formation of
chemical bonds using both a “before picture”
(showing the relative energies of the various
atomic orbitals) and an “after picture”
(showing the relative energies of the molecular
orbitals). We’ll illustrate this with the
molecules H2, He2, H2+ and He2+.
Diatomic Molecules of the First-Period
BO = (e-bond - e-antibond )/2

BO H + = (1-0)/2 = ½
2

BOH = (2-0)/2 = 1
2

BO He + = (2-1)/2 = ½
2

BOHe = (2-2)/2 = 0
2
FIGURE 11-22

•Molecular orbital diagrams for the diatomic molecules and ions of the first-
period elements
 Class Examples
• Draw molecular orbital diagrams for Li2 and
Be2. Using the MO diagrams determine the
bond order for both molecules and, as well,
indicate from the MO diagrams whether the
molecules are diamagnetic or paramagnetic.
Molecular Orbitals of the Second Period Elements

• First period use only 1s orbitals.

• Second period have 2s and 2p orbitals
available.

• p orbital overlap:
– End-on overlap is best – sigma bond (σ).
– Side-on overlap is good – pi bond (π).
 Molecules with 2 Period Atoms
nd

• The simplest possible molecular orbital

diagram that one could imagine for second
row elements having 2p electrons is shown on
the next slide. This slide would necessarily
apply only to homonuclear diatomics. Note the
“symmetrical disposition” of bonding and
nonbonding orbitals.
 FIGURE 11-25 (PART A)

Possible molecular orbital energy-level scheme for diatomic molecules of the second-period elements
 MO Diagrams - Surprises
• The MO diagram presented on the previous
slide does not adequately explain all properties
of diatomic molecules formed from second
period elements. Overlap of 2p atomic orbitals
produces six MOs whose order energy order
can vary with atomic number of the bonded
atoms.
 MO Diagrams – Surprises – C2:
• Two possible MO diagrams are illustrated for
the C2 molecule on the next slide. By
experiment we know that the C2 molecule (4
valence electrons contributed by each C atom
for a total of 8) is diamagnetic. Which of the
MO diagrams accounts for this diamagnetism?
•Experiment shows C2 to be diamagnetic,
supporting a modified energy-level diagram

Expected MO Diagram for C2

Modified MO Diagram for C2

 What do we take from all this?
Three simple kinds of molecular orbitals

1. Sigma (bonding) orbitals (s).

Electrons delocalised along the axis between two nuclei.
These may be represented as shared electrons, e.g. H:H
or H:F; H-H or H-F
2. Non-bonding orbitals (n)
Orbitals that are essentially unchanged from atomic orbitals, and remain
localised on a single atom (unshared).
These may be represented as a pair of electrons on one atom.

3. Sigma star (anti-bonding) orbitals (s*)

Orbitals with a node or nodes along the axis between
two nuclei. These do not contribute to bonding, they
“undo” bonding.
 Molecular Orbital Theory
Diatomic molecules: The bonding in He2
He also has only 1s AO, so the MO diagram for the molecule He2 can be formed in
an identical way, except that there are two electrons in the 1s AO on He.

The bond order in He2 is (2-2)/2 = 0, so

He He2 He
the molecule will not exist.

u* However the cation [He2]+, in which one

of the electrons in the u* MO is
Energy

removed, would have a bond order of

1s 1s (2-1)/2 = ½, so such a cation might be
predicted to exist. The electron
configuration for this cation can be
g
written in the same way as we write
those for atoms except with the MO
labels replacing the AO labels:
[He2]+ = g2u1

Molecular Orbital theory is powerful because it allows us to predict

whether molecules should exist or not and it gives us a clear picture of the
of the electronic structure of any hypothetical molecule that we can
imagine.
 Molecular Orbital Theory
Diatomic molecules: Homonuclear Molecules of the Second Period
Li has both 1s and 2s AO’s, so the MO diagram for the molecule Li2 can be formed in
a similar way to the ones for H2 and He2. The 2s AO’s are not close enough in
energy to interact with the 1s orbitals, so each set can be considered independently.

Li Li2 Li

2u*
The bond order in Li2 is (4-2)/2 = 1, so
2s 2s the molecule could exists. In fact, a
Energy

2g bond energy of 105 kJ/mol has been

measured for this molecule.

Notice that now the labels for the MO’s

have numbers in front of them - this is to
1u* differentiate between the molecular
orbitals that have the same symmetry.
1s 1s
1g
 Molecular Orbital Theory
Diatomic molecules: Homonuclear Molecules of the Second Period
Be also has both 1s and 2s AO’s, so the MO’s for the MO diagram of Be2 are
identical to those of Li2. As in the case of He2, the electrons from Be fill all of the
bonding and antibonding MO’s so the molecule will not exist.

Be Be2 Be The bond order in Be2 is (4-4)/2 = 0, so

the molecule can not exist.

2u* Note:
The shells below the valence shell will
2s 2s always contain an equal number of
bonding and antibonding MO’s so you
Energy

2g
only have to consider the MO’s formed
by the valence orbitals when you want
to determine the bond order in a
molecule!
1u*

1s 1s
1g
 Molecular Orbital Theory
MO diagram for F2 You will typically see the diagrams
F F2 F drawn in this way. The diagram is
only showing the MO’s derived from
3u* the valence electrons because the
pair of MO’s from the 1s orbitals are
much lower in energy and can be
ignored.
1g*
Although the atomic 2p orbitals are
drawn like this: they are
2p (px,py) actually all the same energy and
pz
2p could be drawn like this:
Energy

1u at least for two non-interacting F

atoms.
Notice that there is no mixing of
AO’s of the same symmetry from a
3g
single F atom because there is a
sufficient difference in energy
between the 2s and 2p orbitals in F.

2u* Also notice that the more nodes an

orbital of a given symmetry has, the
higher the energy.
2s 2s
Note: The the sake of simplicity, electrons
2g are not shown in the atomic orbitals.
 Molecular Orbital Theory
MO diagram for F2
F F2 F
Another key feature of such
LUMO 3u* diagrams is that the -type MO’s
formed by the combinations of the px
and py orbitals make degenerate
sets (i.e. they are identical in
HOMO 1g* energy).

2p (px,py)
pz The highest occupied molecular
2p orbitals (HOMOs) are the 1g* pair -
Energy

1u these correspond to some of the

“lone pair” orbitals in the molecule
and this is where F2 will react as an
electron donor.
3g

The lowest unoccupied molecular

orbital (LUMO) is the 3u* orbital -
2u* this is where F2 will react as an
electron acceptor.
2s 2s

2g
 Molecular Orbital Theory
MO diagram for B2
In the MO diagram for B2, there
B B2 B
several differences from that of F2.
3u* Most importantly, the ordering of the
orbitals is changed because of
mixing between the 2s and 2pz
orbitals. From Quantum mechanics:
the closer in energy a given set of
1g* orbitals of the same symmetry, the
larger the amount of mixing that will
2p (px,py)
pz happen between them. This mixing
2p changes the energies of the MO’s
Energy

LUMO 3g that are produced.

The highest occupied molecular
orbitals (HOMOs) are the 1u pair.
HOMO 1u Because the pair of orbitals is
degenerate and there are only two
electrons to fill, them, each MO is
2u* filled by only one electron -
remember Hund’s rule. Sometimes
2s 2s orbitals that are only half-filled are
2g called “singly-occupied molecular
orbtials” (SOMOs). Since there are
two unpaired electrons, B2 is a
paramagnetic (triplet) molecule.