Dr.

Sajjad Hussain [CHEM-305]

MOT
Sumrra Inorganic Chemistry-II
Molecular Orbital
Theory (MOT)
Dr. Sajjad Hussain Sumrra
 Key Points

Molecular Orbital theory

Linear Combination of Atomic Orbitals

Key Features of MOT

Relative Energies of Molecular Orbitals

MOT for Octahedral Complexes

MOT for Tetrahedral Complexes

• Molecular orbital theory describes the distribution of
electrons in molecules in much the same way that the
distribution of electrons in atoms is described using
atomic orbitals. It was proposed early in the 20th
century.
• Using quantum mechanics, the behavior of an electron in
a molecule is still described by a wave function, Ψ,
analogous to the behavior in an atom.
• Just like electrons around isolated atoms, electrons
around atoms in molecules are limited to discrete
(quantized) energies.
• The region of space in which a valence electron in a
molecule is likely to be found is called a molecular
orbital (Ψ2).
• The mathematical process of combining atomic orbitals to
generate molecular orbitals is called the Linear
Combination of Atomic Orbitals (LCAO). The
Schrodinger equation used to describe the electron
behaviour for molecular orbitals can be written in a method
similar to that for atomic orbitals.
• Combining waves can lead to constructive interference,
in which peaks line up with peaks, or destructive
interference, in which peaks line up with troughs.
• In orbitals, the waves are three dimensional, and they
combine with in-phase waves producing regions with a
higher probability of electron density and out-of-phase
waves producing nodes, or regions of no electron density.
(a) When in-phase waves combine,
constructive interference produces a
wave with greater amplitude. (b)
When out-of-phase waves combine,
destructive interference produces a
wave with less (or no) amplitude
Linear Combination of Atomic Orbitals (LCAO)

As per this method, the formation of orbitals is because of

Linear Combination (addition or subtraction) of atomic
orbitals which combine to form the molecule. Consider two
atoms A and B which have atomic orbitals described by the
wave functions ΨA and ΨB.
If the electron cloud of these two atoms overlaps, then we can
obtain the wave function for the molecule by a linear
combination of the atomic orbitals ΨA and ΨB. The below
equation forms two molecular orbitals.
ΨMO = ΨA + ΨB
Bonding Molecular Orbitals:
When the addition of wave function takes place, the type of
molecular orbitals formed are Bonding Molecular Orbitals
and can be represented as ΨMO = ΨA + ΨB. They have lower
energy than atomic orbitals involved.

Anti-Bonding Molecular Orbitals:

When molecular orbital forms by the subtraction of wave
function, the type of molecular orbitals formed are
antibonding Molecular Orbitals and can be represented as
ΨMO = ΨA – ΨB. They have higher energy than atomic
orbitals. Therefore, the combination of two atomic orbitals
results in the formation of two molecular orbitals. They are
the bonding molecular orbital (BMO) and the anti-bonding
molecular orbital (ABMO).
Characteristics of Bonding Molecular Orbitals
• The probability of finding the electron in the
internuclear region of the bonding molecular orbital is
greater than that of combining atomic orbitals.
• The electrons present in the bonding molecular orbital
result in the attraction between the two atoms.
• The bonding molecular orbital has lower energy as a
result of attraction and hence has greater stability than
that of the combining atomic orbitals.
• They are formed by the additive effect of the atomic
orbitals so that the amplitude of the new wave is given
by ΨMO = ΨA + ΨB
They are represented by σ, π, and δ.
Characteristics of Anti-bonding Molecular
Orbitals
• The probability of finding the electron in the internuclear
region decreases in the anti-bonding molecular orbitals.
• The electrons present in the anti-bonding molecular orbital
result in the repulsion between the two atoms.
• The anti-bonding molecular orbitals have higher energy
because of the repulsive forces and lower stability.
• They are formed by the subtractive effect of the atomic
orbitals. The amplitude of the new wave is given by;
ΨMO ´= ΨA – ΨB
• They are represented by σ∗, π∗, δ∗
 Key Features of Molecular Orbital Theory

• Molecular orbital (MO) theory considers the overlap of

atomic orbitals, of matching symmetry and comparable
energy, to form molecular orbitals.
• When atomic orbital wave functions are combined, they
generate equal numbers of bonding and antibonding
molecular orbitals.
• The bonding MO is always lower in energy than the
corresponding antibonding MO.
• Electrons occupy the molecular orbitals in order of their
increasing energy in accordance with the aufbau principal.
• Each line in the diagram represents an orbital.
• The molecular orbital volume encompasses the whole
molecule.
• The electrons fill the molecular orbitals of molecules
like electrons fill atomic orbitals in atoms.
• Electrons go into the lowest energy orbital available to
form lowest potential energy for the molecule.
• The maximum number of electrons in each molecular
orbital is two. (Pauli exclusion principle)
• One electron goes into orbitals of equal energy, with
parallel spin, before they begin to pair up. (Hund's
Rule.)
 Relative Energies of Molecular Orbitals

• Bonding Molecular Orbitals (BMO) – Energy of

Bonding Molecular Orbitals is less than that of Anti
Bonding Molecular Orbitals. This is because of the
increase in the attraction of both the nuclei for both the
electron (of the combining atom).

• Anti-Bonding Molecular Orbitals (ABMO) – Energy of

Anti Bonding Molecular Orbitals is higher than Bonding
Molecular Orbitals. This is because the electron tries to
move away from the nuclei and are in a repulsive state.
 Atomic and Molecular Orbitals
• The two 1s atomic orbitals combine to form two molecular
orbitals, one bonding (s) and one antibonding (s*).
• This is an illustration of molecular orbital diagram of H2.

•.Notice that one

electron from each
atom is being
“shared” to form a
covalent bond. This
is an example of
orbital mixing.
Molecular Orbital Diagram (HF)
MO Diagram for O2, O2 -, O2 +
• Molecular orbital theory (MOT) provides an
explanation of chemical bonding that accounts for the
paramagnetism of the oxygen molecule.
• It also explains the bonding in a number of other
molecules, such as violations of the octet rule.
• Additionally, it provides a model for describing the
energies of electrons in a molecule and the probable
location of these electrons.
• MO theory also helps us understand why some
substances are electrical conductors, others are
semiconductors, and still others are insulators.
Paramagnetic Nature of the Oxygen Molecule
 Bond Order

The number of bonds between a pair of atoms is called

the bond order. Bond orders can be calculated from Lewis
structures using the following formula;

Bond Order =
Examples of Bond Orders for Different Oxygen Species
Examples of Bond Orders and Magnetism
 Molecular Orbital Theory of Octahedral
Transition Metal Complexes

• The characteristics of transition metal-ligand bonds

become clear by an analysis of the molecular orbitals of a
3d metal coordinated by six identical ligands in octahedral
complexes [ML6].
• As the result of the interaction between the metal d and
ligand orbitals, bonding, non-bonding and anti-bonding
complex molecular orbitals are formed.
• Generally, the energy levels of the ligand orbitals are
lower than those of the metal orbitals, bonding orbitals
have more ligand character and non-bonding and anti-
bonding orbitals have more metal character.
• The MO energy level diagrams for metal complexes are
much more complicated than those for simple diatomic
molecules.
• Ligand orbitals are, in general, of lower energy than the
metal orbitals, and hence the bonds have some ionic
character.
• Bonding MO’s, in general, are closer in energy to ligand
orbitals than to metal orbitals and are more like the ligand
orbitals; placing metal electrons in these MO’s thus
transfers electronic charge from metal to ligands.
• Two d orbitals (the eg orbitals, dx2_y2 and dz2), the 4s, and
the three 4p orbitals are oriented along the x, y, and z
axes where the ligands are located.
• Therefore, orbital overlap with the ligand AO’s results,
and six bonding and six antibonding MO’s are formed.

• The t2g (dxy, dxz, and dyz) orbitals do not point at ligand
orbitals and hence are not involved in σ bonding.
• Their energy is unchanged, and they are called
nonbonding orbitals.
Octahedral Complexes Having Strong Ligands
(Low Spin Complexes)

In the case of LS octahedral complexes, 12 electrons

donated by 6 ligands will occupy 6 BMO’s and the
electrons present in the d-orbitals of the free metal ion will
go to t2g non-bonding orbitals until these orbitals are
completely filled and if required , the extra electrons of d-
orbitals will occupy eg*ABMO’s. Thus, the distribution of
electrons in various BMO’s, non-bonding d-orbitals and
eg*ABMO’s of octahedral complexes of dx ion (x = 1-10)
having strong ligands (LS complexes) is given in table;
 Octahedral Complexes Having Weak Ligands
(High Spin Complexes)

In the case of HS octahedral complexes, 12 electrons

donated by 6 ligands will occupy 6 BMO’s.
Now since the difference between non-bonding orbitals t2g
and eg*ABMO’s is small. As a result, electrons present –n
d-orbitals of free metal ion will go to t2g non-bonding
orbitals and eg*ABMO’s according to Hund’s rule. Thus,
the distribution of electrons in various BMO’s, non-bonding
d-orbitals and eg*ABMO’s of octahedral complexes of dx
ion (x = 1-10) having weak ligands (HS complexes) is given
in table;
Formation of MO for s-orbital
Formation of MO of for p-orbitals
Formation of MO for d-orbitals
Formation Of Sigma Molecular Orbitals In Octahedral Complex
The molecular orbital
diagram is consistent
with the crystal field
approach.
Note that the t2g set of
orbitals is non-bonding,
and the eg set of orbitals
is antibonding.
 The electrons
from the ligands
(12 electrons
from 6 ligands in
octahedral
complexes) will
{ fill the lower
bonding orbitals.
{
The electrons from
the 4s and 3d orbitals
of the metal (in the
first transition row)
will occupy the
middle portion of the
diagram.
Formation Of Sigma Molecular Orbitals In [Co(NH3)6] +3 ion
Formation Of Sigma Molecular Orbitals In [Ti(H2O)6]+3 ion
Formation Of Sigma Molecular Orbitals In [CoF6]-3 ion
 Molecular Orbital Theory for Tetrahedral
Transition Metal Complexes

• The characteristics of transition metal-ligand bonds

become clear by an analysis of the molecular orbitals of a
3d metal coordinated by four identical ligands in
octahedral complexes [ML4].
• As the result of the interaction between the metal d and
ligand orbitals, bonding, non-bonding and anti-bonding
complex molecular orbitals are formed.
• Generally, the energy levels of the ligand orbitals are
lower than those of the metal orbitals, bonding orbitals
have more ligand character and non-bonding and anti-
bonding orbitals have more metal character.
Formation Of Sigma Molecular Orbitals In Tetrahedral Complex
Formation Of Sigma Molecular Orbitals In [Ni(CO)4] ion
MOT can explain the influence of π bonds on the stability
of metal complexes and on the magnitude of the crystal
field splitting provided by ligands.
Example:
• In [Fe(CN)6]4– and a variety of other metal complexes,
both σ and π bonding occur. In the σ bond, the ligand
acts as a Lewis base and shares a pair of electrons with
an empty eg orbital.
• In the π bond, CN– ion acts as a Lewis acid and accepts
electrons from the filled t2g orbital of the metal. The
presence of π bonding as well as σ bonding strengthens
the metal–ligand bond and contributes to the unusual
stability of the [Fe(CN)6]4– ion.
The σ and π bonds in [Fe(CN)6]4–.The π bond makes
use of a filled d orbital of Fe2+ and an empty
antibonding π* orbital of CN–
• In oxyanions, such as MnO4–, σ and π bonding are also
both important. In this case, the ligand (oxygen) provides
the electrons for the π bond.
• The large crystal fields that are provided by CN–, CO,
and other π bonding ligands can be explained in this
manner.
• The t2g orbitals of a metal in an octahedral complex are
oriented correctly for π bonding. The t2g orbitals point
between ligands and hence cannot form σ bonds.
• In a π bond with a ligand such as CN–, t2g electrons are
partially transferred to the ligand. This process (a
bonding interaction) lowers the energy of the t2g orbitals.
Sigma donation and pi donation
Overview of MOT
Conclusion:

• In conclusion, note that all three of these theories are, at

best, only good approximations.
• All three can account qualitatively for many features of
metal complexes; all three are used currently, and one or
the other may be most convenient for a given
application.
• The most versatile is MOT. Unfortunately, it is also the
most complicated.