1

Molecular Orbital Theory

In principle, the electronic structure of
molecules can be worked out in the same way
as for atoms:
solve the Schrdinger equation
This gives molecular orbitals rather than atomic
orbitals
But: It is difficult to solve the Schrdinger
equation for molecular species (only through
approximation!)
LCAO approximation
LCAO = Linear Combination of Atomic Orbitals
The wavefunctions of molecular orbitals can be
approximated by taking linear combinations of
atomic orbitals

=
1
2

1s
(H
a
) +
1s
(H
b
)
[ ]
linear combination (addition) of the wavefunction from two 1s orbitals
2
LCAO approximation
A second MO (molecular orbital) can be obtained
via subtraction of two AOs

*
=
1
2

1s
(H
a
)
1s
(H
b
)
[ ]
linear combination (subtraction) of the wavefunction from two 1s orbitals
nodal plane
the resulting wavefunction has a nodal plane perpendicular to the
HH bond axis (electron density = zero); the energy of an electron in
this orbital is higher compared to the additive linear combination =
antibonding orbital
Bonding in H
2
Take two 1s orbitals as the basis
Get two MOs

+
=
1s
(A) +
1s
(B)

-
=
1s
(A) -
1s
(B)
One electron in BO
gives 2.6 eV bond
energy but two
electrons give only
4.5 eV. Why?
3
Occupying the bonding
orbital(s) of a molecule
makes the interaction
between atoms attractive
(they stick together)
Occupying antibonding
orbitals makes the
interaction between atoms
repulsive
Potentials for occupied bonding and
antibonding orbitals
First Period Diatomic Molecules
4
Linear combinations of p
z
orbitals
Addition of two p
z
AOs results a bonding
p
MO,
subtraction will give an antibonding
p
* MO with a
nodal plane perpendicular to the bond axis

*
=
1
2

2 pz
(H
a
)
2 pz
(H
b
)
[ ]

=
1
2

2 pz
(H
a
) +
2 pz
(H
b
)
[ ]
nodal plane
Linear combinations of p
x
and p
y
orbitals
Addition of two p
x
(or p
y
) AOs results a bonding
p
MO
containing a nodal plane along the bond axis:
Subtraction results an antibonding
p
* MO with two nodal
planes: one plane perpendicular and one parallel to the bond
axis
5
Classifying orbitals by symmetry
Orbitals in diatomics can be classified according to their
rotational symmetry characteristics as , or . These
classifications are strictly only valid for diatomics, but we also
use them to describe bonds between pairs of atoms in
polyatomic molecules.
orbitals orbitals
orbitals
Found in quadruply bonded
species such as [Re
2
Cl
8
]
2-
What types of bond can be formed?
The type of bond (, or ) that can be formed
depends up on the available atomic orbital types
6
Electron density distribution of
different MOs
Overlap between orbitals
The extent to which
orbitals overlap can be
evaluated using an
overlap integral S.
S = 0 indicates that the
orbitals do not
overlap/interact with one
another
S depends on the
symmetry of the orbital
7
Overlap 2
Do the orbital
combinations on the
right have S = 0, S >0
or S< 0?
Homonuclear diatomic energy level diagram
energy
Electrons are filled according to the same guidelines
as for multielectron elements (Aufbau principle)
8
Full energy
level diagram
for second row
diatomics
Rules for the use of MOs
When two AOs mix, two MOs will be produced
For mixing AOs must have similar energies
Each orbital can have a total of two electrons
(Pauli principle)
Lowest energy orbitals are filled first (Aufbau
principle)
Unpaired electrons have parallel spin (Hunds
rule)
Bond order = 1/2 (bonding electrons antibonding electrons)
9
Molecular oxygen
energy
AOs AOs
Bond order = 2
2 unpaired electrons > paramagnetic
Molecular fluorine
energy
AOs AOs
Bond order = 1
0 unpaired electrons > diamagnetic
10
Neon
energy
AOs AOs
Bond order = 0
> not a stable molecule!
Orbital Mixing
Orbitals with similar energy interact, if they have the
appropriate symmetries
The
2p
and
2s
orbitals are symmetry related and give
rise to two new orbitals, one with higher and one with
lower energy
11
energy
Note: With mixing the
g
orbital is higher in energy than the
2p
orbitals
Effect of orbital mixing
Ungerade or gerade ?
MOs in molecules that are centrosymmetric can
be classified as (g) or (u)
Useful for predicting spectroscopic transitions etc.
(g) implies that the wavefunction does not change sign
on inversion through the center of the molecule. (u)
means that it does change sign
12
Photoelectron Spectroscopy (PES)
UV-photoelectron spectroscopy can be used to verify
the MO energy level diagram
Molecules are ionized with monochromatic light:
N
2(g)
+ h N
2(g)
+
+ e

The kinetic energy of the resulting photoelectrons are

measured and a plot of number of photoelectrons versus
photoelectron energy drawn (this is a photoelectron
spectrum)
The PES experiment
13
The PES spectrum of N
2
Note nitrogen atoms have a first ionization energy of 14.5 eV
Molecular Nitrogen
According to calculations the
g
orbital is higher in
energy than the two
2p
orbitals:
energy
Bond order = 3
no unpaired electrons > diamagnetic
14
Beryllium (Be
2
) Molecule
energy
Bond order = 0 not a stable molecule
Was detected at very low temperature; bond energy = 4kJmol
1
Lithium (Li
2
) Molecule
energy
Bond order = 1; known in the gas phase
No unpaired electrons diamagnetic
15
Bond Order vs. Bond Length & Energy
Hetronuclear diatomics
The contributions to the MO from each of
the atoms is unequal
= c
A
(A) + c
B
(B) +.......
The more electronegative atom contributes
strongly to the bonding orbital
The less electronegative atom contributes
strongly to the anti-bonding orbital
gives rise to polarity
16
Orbital mixing
The difference in energy
between orbitals on
different atoms leads to
reduced mixing
The reduced mixing does
not imply weaker bonding
Heteronuclear Molecules
The relative energy of the bonding orbitals
determines the magnitude of the covalent bond
energy (E
cov
):
17
Hydrogen Fluoride
In H-F the 1s orbital of H is energetically well above the 1s and
2s orbitals of F
it interacts only with the 2p
z
orbital (all remaining electrons are in non-
bonding orbitals!)
non-bonding MOs
Lithium Fluoride
As the polarity difference between two atoms increases, the
orbital energy difference also increases
electrons shift towards the more electronegative atom
Limiting case: Ionic compounds
Ionic crystal:
Ions are held together in a
3-dimensional lattice by
combination of electrostatic and
covalent interactions
There are no directional
bonds
18
Carbon monoxide
Note that the HOMO and LUMO
are largely on C. Important for
metal carbonyl formation
Molecular Orbitals of Polyatomic Molecules
Concept of linear combination can be also
applied to polyatomic molecules
the resulting MOs are delocalized over the entire
molecule
Symmetry analysis by group theory predicts
those linear combinations, which lead to
bonding, anti-bonding or non-bonding MOs
The energy of the resulting MOs is measured
via photoelectron spectroscopy or estimated
with quantum chemical calculations
19
Beryllium Dihydride (BeH
2
)
VSEPR analysis: linear geometry
Set of AOs:
Be: one 2s, three 2p
H: two 1s orbitals
Note: the 2p
x
and 2p
y
orbitals result non-bonding interactions
Form group orbitals with 1s orbitals of H and H:

A
=
1s
(H) +
1s
(H' )

B
=
1s
(H)
1s
(H' )
Overlap with 2s (Be)
Overlap with 2p
z
(Be)
Group Orbitals Interact with Be AOs:

A
interacts with the 2s orbital of Be to form a bonding (
s
) and
anti-bonding (
s
*) orbital:

B
interacts with the 2p
z
orbital of Be to form a bonding (
p
) and
anti-bonding (
p
*) orbital:
20
BeH
2
Energy Level Diagram
Group orbitals

B
energy
MOs of Water (H
2
O)
VSEPR analysis: bent geometry
Set of AOs:
O: one 2s, three 2p
H: two 1s orbitals
Note: the 2p
y
orbital is non-bonding
Form goup orbitals with 1s orbitals of H and H:

A
=
1s
(H) +
1s
(H' )

B
=
1s
(H)
1s
(H' )
Overlap with 2s, 2p
z
Overlap with 2p
x
(O)
H
2
O in the x-z plane with z
bisecting the H-O-H angle
21
The Two
A
Group Orbital Interactions:

A
interacts with two AOs of Oxygen: The 2s and 2p
z
orbital:
this results in one bonding, one anti-bonding and
one non-bonding (approximately) orbital:

A
2p
z
2s
Oxygen AOs
(Group Orbital)

s,z
*

s,z

s,z
nb
The
B
Group Orbital Interaction:

B
interacts with the 2p
x
orbital of oxygen to form a
bonding (
x
) and anti-bonding (
x
*) orbital:

B
2p
x
22
To Give the Final Energy Level Diagram...

B
energy
Group orbitals
H
2
O MO shapes
23
Composition of NH
3
MOs
MO diagram + PES for NH
3
24
H
3
+
This species is postulated as an intermediate in
some reactions
It is the simplest triatomic molecule
Linear H
3
1 =
1s
(A) + 2
1/2

1s
(B) +
1s
(C)
2 =
1s
(A) -
1s
(C)
3 =
1s
(A) - 2
1/2

1s
(B) +
1s
(C)
25
Three center two electron bonds
The orbitals in H
3
are delocalized over the
entire molecule
In H
3
+
2 electrons hold the molecule together
this is an example of a three center two electron
bond
Diborane and electron deficient compounds
B
2
H
6
is a compound that you can not draw a
reasonable Lewis structure for !
Electron deficient as
the three atoms
forming the B-H-B
bridge are held
together using only
two electrons
26
SF
6
and hypervalence
XeF
2
and electron excess compounds
The electronic structure of XeF
2
and its
stability can be rationalized by invoking a 3
center 4 electron bond
27
MO s for Polyatomic chains
Constructing MOs for polyatomic chains
28
MOs in one-dimensional arrays of like orbitals
There will be as many MOs as orbitals in the array. Every molecular orbital is
characterized by a specific pattern of nodes,
The lowest energy orbital will have zero nodes, the next highest will have one node, the
next two, etc. The highest energy molecular orbital will have n-1 nodes, where n is the
number of atomic orbitals involved.
When symmetrical placement of a node causes it to fall on an atom, then that atom does
not contribute to the molecular orbital.
E
Bonding and electronic structure of
metals and other solids
Any successful model for the bonding in
metals must be able to explain
- good thermal and electrical conductivity
Molecular Orbital theory can be extended
to solid materials including metals
29
Molecules of metal atoms
Band structure
30
Metals, insulators and semiconductors
Electrical conductivity
Solids only conduct electrons when they
have unpaired electrons in orbitals
for metal this is only true for electrons near to
the Fermi level
for semiconductors the presence of impurities
increases the number of electrons that are
unpaired
31
Temperature dependence
Semiconductor band gaps
5.4 Diamond 1.5 GaAs
4.6 AlN 1.3 InP
3.9 ZnS 1.1 Si
3.4 SrTiO
3
0.8 GaSb
3.4 ZnO 0.7 Ge
2.9 GaP 0.6 ZnSb
2.8 ZnSe 0.4 InAs
2.6 CdS 0.3 PbS
2.4 InN 0.3 Te
2.2 Cu
2
O 0.2 PbTe
1.8 Se 0.2 InSb
1.6 CdTe 0.0 -Sn
E
gap
, eV Compound E
gap
, eV Compound
32
Light-emitting diodes