Gokul Ganesan 1

Inorganic Chemistry

MOLECULAR ORBITAL THEORY

 The MOT was put forth by F. Hund & R.S. Mulliken in 1930’s and later further
developed by I.E. Lennard-Jones & Charles Coulson.
 The wave mechanical treatment of a covalent bond according to MOT distinctly differs
in the conceptual approaches to the basic structural model of a molecule. According to
MOT, the nuclei of the two atoms lie at appropriate distance and all the atomic orbitals
[and not just valence orbitals which are half-filled] of one atom overlap with the atomic
orbitals of the other atom provided the overlapping orbitals are of the same symmetry
and of similar energy..
 The assumption in MOT is that if two nuclei are positioned at an equilibrium distance,
and electrons are added, they will go into molecular orbitals that are in many ways
analogous to atomic orbitals.
 The Schrodinger equation cannot be exactly solved for the simplest multi-electron
system of a Helium atom. Approximate methods were required to solve the wave
equation in such systems.
 One of the approximate methods to solve the electron wave functions in molecules is
LCAO – Linear Combination of Atomic Orbitals. LCAO assumes that we can
approximate the correct molecular orbital by the linear combination of atomic orbitals of
the combining atoms.
 The basic principles of MOT are as follows:
1. When nuclei of two atoms come close to each other, their atomic orbitals interact
leading to the formation of molecular orbitals. The atomic orbitals of the atoms in a
molecule completely lose their identity after the formation of molecular orbitals. The
number of molecular orbitals is the same as the total number of combining
atomic orbitals.
2. Each molecular orbital is described by a wave function ψ, known as molecular
orbital wave function.
3. The square of the molecular orbital wave function, ψ2 represents the probability
density or electron charge density in the molecule.
4. Each molecular orbital wave function ψ is associated with a set of quantum
numbers which determine the energy and the shape of the MO.
5. Each ψ is associated with a definite energy value and the total energy of the
molecule is the sum of the energies of occupied molecular orbitals.
6. Electrons fill the molecular orbitals in the same way as they fill the atomic orbitals
following the aufbau principle, Pauli’s exclusion principle and the Hund’s rule of
maximum multiplicity.
7. Each electron in a molecular orbital belongs to all the nuclei present in the molecule.
8. Each electron moving in a molecular orbital has a spin of +½ or –½.
 In the previous note on VBT, a text box gave us the principle differences underlying the
assumptions involved in VBT & MOT. It is worthwhile to recollect that valence bond
treatment begins with bringing two hydrogen atoms from infinite distance to the bond
length equilibrium distance. The MO approach however, starts with the two hydrogen
 Gokul Ganesan 2
Inorganic Chemistry

nuclei at mean distance from one another as they are likely to be when a bond is formed.
Electrons are then visualized to be added to this two nuclei system.
 Consider a H2+ ion consisting of two H nuclei designated as HA & HB, the single electron
is supposed to be moving in a molecular orbital formed by the interaction of atomic
orbitals of two hydrogen atoms.

e-

HA HB
H2+

e- HA HB HA HB e-

Situation 1 Situation 2

The electron is moving under the influence of both the nuclei HA & HB. When, at some
instant, it comes nearer to nucleus A (situation 1), the electron would behave as if it was
moving in the atomic orbital of HA. The motion of the electron could then be
approximated to ϕA (the unmixed atomic orbital wave function of HA). Similarly, when
the electron is nearer to nucleus B (situation 2), its motion could be approximated to ϕB.
In between these two situations, the electron would be under the influence of both the
nuclei and its motion could be described by a wave function which is a linear
combination of ϕA & ϕB.
 The rationale behind this approximation is that most of the time the electrons will be
nearer and hence controlled by one or the other of the two nuclei and when this is so, the
molecular orbitals should be very nearly the same as the atomic orbital for that atom.

Where & are the wave functions for the atomic orbitals of atom A and atom B.
is lower in energy than the corresponding atomic orbitals and is termed Bonding
Molecular Orbital (BMO) and is higher in energy as compared to the
corresponding atomic orbitals and is termed Antibonding Molecular Orbital (ABMO).
In addition, it is also possible to generate a molecular orbital that has the same energy as
the initial atomic orbitals. In this case, occupation of this orbital neither stabilizes nor
destabilizes the molecule and so it is described as a Non-Bonding Molecular Orbital
(NBMO).
 The electron distribution in a molecule is given as by the square of the wave functions,
hence the electron distribution in a molecule with molecular orbitals & can be
given as follows:
 Gokul Ganesan 3
Inorganic Chemistry

The difference between the two probability functions lies in the cross term 2 . The
integral ∫ is known as the overlap integral, S. In the bonding orbital, the
overlap is positive and the electron density between the nuclei is increased, whereas in
the antibonding orbital the electron density between the nuclei is decreased.

2
b b

2
a a

The dotted lines in each of the wave functions ψb & ψa are the individual atomic orbital
wave functions. The difference between the solid curve and the dotted lines is the
overlap integral, which increases the electron density in between the two nuclei in the
bonding molecular orbital and decreases the electron density to the extent that there is a
zero probability of finding the electron in the internuclear axis for an antibonding
molecular orbital.
 As per the above discussion, it is amply clear that for bonding, S>0; and for antibonding,
S<0. The condition S=0 is termed as non-bonding and corresponds to no interaction
between the orbitals.
In s orbitals, the sign of the wave function is the same everywhere (with the exception of
small intermodal regions for n>1), and so there is no problem with matching the sign of
the wave functions to achieve a positive overlap. With p and d orbitals, however, there
are several possible ways of arranging the orbitals, some resulting in positive overlap,
some resulting in negative overlap and some in which the overlap is exactly zero.
 Gokul Ganesan 4
Inorganic Chemistry
 Gokul Ganesan 5
Inorganic Chemistry

 The orbitals which are cylindrically symmetrical about the internuclear axis are called σ
molecular orbitals, analogous to an s orbital, the atomic orbital of highest symmetry. If
there is a nodal plane along the internuclear axis, a π bond results. In δ bonds, there are
two nodal planes, one along the internulcear axis and the other in a mutually
perpendicular plane.
 Gokul Ganesan 6
Inorganic Chemistry

 Molecular Orbitals in Homonuclear diatomic molecules: There are two criteria that must
be met for the formation of bonding molecular orbitals. One is that the overlap between
the atomic orbitals must be positive. Furthermore, in order that there is effective
interaction between orbitals on different atoms, the energies of the atomic orbitals must
be approximately the same. For now, we will assume that MO’s will form from
corresponding orbitals on the two atoms (i.e; 1s+1s; 2s+2s etc.). We shall soon see that
under some circumstances this assumption will have to be modified. When we combine
the atomic orbitals in this way, the energy levels shown below are obtained. The
appropriate combinations are:

The atomic 2s orbitals form a similar set of σ and σ* molecular orbitals like the 1s
orbitals of hydrogen molecule. The atomic p orbtials can form σ bond from direct
(“head on”) overlap of the pz orbtials and two π bonds from parallel overlap of the py
and px orbitals. Because the overlap is greater in the former case, we should expect the
covalent energy to be greater; also σ bonds are stronger than π bonds. Hence the
orbital is stabilized (lowered in energy) as compared to & molecular orbitals,
and conversely the corresponding antibonding orbital is raised accordingly. [NOTE:
Order is different to account for s-p mixing for elements before
 The aufbau’s table for filling up of molecular orbitals is given on the next page. The
order of energies changes slightly for boron, carbon and nitrogen due to s-p mixing. As
mentioned earlier, the Pauli’s exclusion principle and Hund’s rule of multiplicity must be
borne out whilst filling molecular orbitals. The routine information derived from MO
diagram involve
1. Electronic configuration: The electronic configuration of molecules helps in
understanding bonding and ionization in molecules.
2. Bond order = ½ (Nb – Na) [Half of the difference between number of electrons
filling up the BMO’s and the number of electrons filling up ABMO’s]
3. Magnetic properties: There are two types of magnetic behaviour, paramagnetic &
diamagnetic. Paramagnetic compounds are attracted by an external magnetic field.
This attraction is a consequence of one or more unpaired electrons behaving as tiny
magnets. Diamagnetic compounds on the other hand have no unpaired electrons and
are repelled slightly by magnetic fields.
 Gokul Ganesan 7
Inorganic Chemistry

A.O’s M.O’s A.O’s

σ*2pz

π*2px π*2py

2px 2py 2pz 2pz 2py 2px

π2px π2py

σ2pz
Energy

σ*2s

2s 2s

σ2s

σ*1s

1s 1s

σ1s

 H2 molecule: MO Diagram – [Atomic no: 1; 1s1]

M.O’s
A.O’s A.O’s

σ*1s

↑ ↑
Energy

1s 1s

↑↓
σ1s
Electronic configuration: σ1s2
 Gokul Ganesan 8
Inorganic Chemistry

Bond Order: ½ (2 – 0) = 1
Magnetic Property: Diamagnetic
H2 is a stable molecule with bond length 74.2 pm and bond dissociation energy of 458
kJ/mol. H2+ has been detected in low pressure gas discharge systems but is less stable
than H2 indicated by its bond length of 106 pm and dissociation energy of 269 kJ/mol
 He2 molecule: MO Diagram – [Atomic no: 2; 1s2]
M.O’s
A.O’s A.O’s
↑↓
σ*1s

↑↓ ↑↓
Energy

1s 1s

↑↓
σ1s
Electronic configuration: σ1s2 σ*1s2
Bond order = ½ (2 – 2) = 0
The molecule He2 is unknown since the number of antibonding electrons is equal to the
number of bonding electrons and the net bond order is zero. This indicates zero bonding
energy and hence two helium atoms in a molecule will not remain together but fly apart.
Hence Helium exists as a monoatomic gas.
If Helium ionized, it is possible to form diatomic helium molecule-ions, He2+. Such a
molecule will contain three electrons, two bonding and one antibonding, for a net bond
order of one-half. Such a species, although held together with only about one-half the
bonding energy of the hydrogen molecule should be expect to exist. In fact it does, and it
has been observed spectroscopically in highly energetic situations sufficient to ionize
helium.
 Li2 molecule: MO Diagram – M.O’s [Atomic no: 3; 1s2 2s1]
A.O’s A.O’s
σ*2s

↑ ↑
2s 2s

↑↓
σ2s

↑↓
Energy

σ*1s

↑↓ ↑↓
1s 1s

↑↓
σ1s
 Gokul Ganesan 9
Inorganic Chemistry

Electronic configuration: σ1s2 σ*1s2 σ2s2 or KK σ2s2

Bond order = ½ (4 – 2) = 1
Magnetic property: Diamagnetic
Lithium exists as its diatomic molecule in the gas phase. The bond dissociation energy of
Li2 is 105 kJ/mol and the bond length is 267 pm which is in synch with the calculated
bond order of 1.
 Be2 molecule: MO Diagram – [Atomic no: 4; 1s2 2s2]
M.O’s

A.O’s ↑↓ A.O’s
σ*2s

↑↓ ↑↓
2s 2s

↑↓
σ2s

↑↓
Energy

σ*1s

↑↓ ↑↓
1s 1s

↑↓
σ1s
Electronic configuration: σ1s2 σ*1s2 σ2s2 σ*2s2 or KK σ2s2 σ*2s2
Bond order = ½ (4 – 4) = 0
Be2 molecule could not be traced even in gas phase. This is in synch with our predictions
of non-existence of Be2 molecule owing to its zero bond order.
 B2 molecule: MO Diagram – [Atomic no: 5; 1s2 2s2 2p1]
The energy difference between the 2s and 2p orbitals is less in boron, carbon and
nitrogen and varies with effective nuclear charge. With a larger Z*, as in fluorine, the
energy difference is greater and mixing may again be neglected. The difference in energy
between the 2s and 2p levels dramatically increases from 200 kJ/mol in lithium atom to
about 2500 kJ/mol in fluorine. In case of the elements to the left of the series, the lower
effective nuclear charge allows the 2s and 2p orbitals to come sufficiently close to mix.
This phenomenon is the equivalent of hybridization in VBT.
Another way to view this phenomenon is to ignore s-p mixing in the initial construction
of molecular orbitals but then recognize that MO’s of the same symmetry will interact if
they are close enough in energy. Thus the σg(2s) and σg(2p) molecular orbitals in a
molecule such as B2 will interact. As a result, the lower energy orbital [σg(2s)] will be
stabilized while the higher energy one [σg(2p)] will become less stable. This leads to a
reversal in the energy ordering of the πu(2p) and σg(2p) molecular orbitals compared to
the case for molecules such as F2, where essentially no mixing occurs. There will also be
 Gokul Ganesan 10
Inorganic Chemistry

some interaction between the σ*u(2s) and the σ*u(2p) but since these orbitals do not
approach each other closely in energy, the interaction will be negligible.
[Note: The notations g and u stand for gerade and ungerade and will be covered later on.]
 Gokul Ganesan 11
Inorganic Chemistry

A.O’s M.O’s A.O’s

σ*2pz

π*2px π*2py

↑ ↑
2px 2py 2pz 2pz 2py 2px

σ2pz
↑ ↑
π2px π2py
Energy

↑↓
σ*2s

↑↓ ↑↓
2s 2s

↑↓
σ2s

Electronic configuration: σ1s2 σ*1s2 σ2s2 σ*2s2 π2p2

Bond order: ½ (6 – 4) = 1
Magnetic property: Paramagnetic
B2 is found only in the gas phase and is paramagnetic. It is a good example of the energy
level shift caused by the mixing of s and p orbitals. In the absence of mixing, the σ (2p)
orbital is expected to be lower in energy than the π (2p) orbitals and the resulting
molecule would be diamagnetic. However, mixing of the σ (2s) and σ (2p) orbital lowers
the energy of the σ (2s) and increases the energy of the σ (2p) orbital to a higher level
than the π orbitals, giving the order of energies as shown. As a result, the last two
electrons are unpaired in the degenerate π orbitals, and the molecule is paramagnetic.
The bond length of B2 is 159 pm and its dissociation energy is 289 kJ/mol.
 C2 molecule: MO Diagram – [Atomic no: 6; 1s2 2s2 2p2]
 Gokul Ganesan 12
Inorganic Chemistry

A.O’s M.O’s A.O’s

σ*2pz

π*2px π*2py

↑ ↑ ↑ ↑
2px 2py 2pz 2pz 2py 2px

σ2pz
↑↓ ↑↓
π2px π2py
Energy

↑↓
σ*2s

↑↓ ↑↓
2s 2s

↑↓
σ2s

Electronic configuration: σ1s2 σ*1s2 σ2s2 σ*2s2 π2p4

Bond order: ½ (6 – 2) = 2
Magnetic property: Diamagnetic
The molecule of C2 is unusual in that it has two π bonds but no σ bond. The bond
dissociation energies of B2, C2 & N2 increase steadily, indicating single, double and triple
bonds with increasing atomic number. Although C2 is not commonly encountered
chemical species, the acetylide ion, C22- is well known. According to the molecular
orbital model, it should have a bond order of 3. [Activity: Write the electronic
configuration of C22- and calculate its bond order.] This is supported by similar C-C
distances in acetylene and calcium carbide.
C – C distance (pm)
C = C (gas phase) 132
H–C≡C–H 120.5
CaC2 119.1

 N2 molecule: MO Diagram – [Atomic no: 7; 1s2 2s2 2p3]

 Gokul Ganesan 13
Inorganic Chemistry

A.O’s M.O’s A.O’s

σ*2pz

π*2px π*2py

↑ ↑ ↑ ↑ ↑ ↑
2px 2py 2pz 2pz 2py 2px

↑↓
σ2pz
↑↓ ↑↓
π2px π2py
Energy

↑↓
σ*2s

↑↓ ↑↓
2s 2s

↑↓
σ2s

Electronic configuration: σ1s2 σ*1s2 σ2s2 σ*2s2 π2p4 σ2p2

Bond order: ½ (10 – 4) = 3
Magnetic property: Diamagnetic
Nitrogen has a triple bond according to both the Lewis and the molecular orbital models.
This is in agreement with its very short N-N distance of 109.8 pm and extremely high
bond dissociation energy of 942 kJ/mol. The shielding effect and electron-electron
interactions cause an increase in the difference between the 2s and 2p orbital energies as
the nuclear charge increases. As a result, the 2s and 2p levels of Nitrogen interact much
less as compared to boron and carbon.
It is also interesting to note that the magnetic properties of B2 and C2 are strong
evidences for a reversal in the order of energies of the σ and the π energy levels.
However, both the electronic configurations would lead to diamagnetism which is the
experimentally observed magnetic property.
Although the MO diagram above for Nitrogen is widely accepted, the order of energies
of these orbitals has been a matter of controversy.
 O2 molecule: MO Diagram – [Atomic no: 8; 1s2 2s2 2p4]
 Gokul Ganesan 14
Inorganic Chemistry

A.O’s M.O’s A.O’s

σ*2pz

↑ ↑
π*2px π*2py

↑ ↑ ↑↓ ↑↓ ↑ ↑
2px 2py 2pz 2pz 2py 2px

↑↓ ↑↓
π2px π2py

↑↓
σ2pz
Energy

↑↓
σ*2s

↑↓ ↑↓
2s 2s

↑↓
σ2s

Electronic configuration: σ1s2 σ*1s2 σ2s2 σ*2s2 σ2p2 π2p4 π*2p2

Bond order: ½ (10 – 6) = 2
Magnetic property: Paramagnetic
One of the biggest successes of Molecular Orbital Theory is exhibited in the MO
treatment of oxygen molecule. Oxygen is paramagnetic which is contrary to what VBT
predicts. However the predictions of MOT are in synch with the experimental
observation of its magnetic property.
Internuclear
Species Bond order
distance (pm)
O2 + 2.5 112.3
O2 2.0 120.07
-
O2 1.5 128
2-
O2 1.0 149

The Oxygen molecule has a double bond resulting from two σ bonding electrons, four π
bonding and two π antibonding electrons. The bond length is 120 pm. Addition of two
electrons to the oxygen molecule results in the well-known peroxide ion O22-.
 Gokul Ganesan 15
Inorganic Chemistry

According to its MO diagram, the two electrons will enter the π* orbitals, decreasing the
bond order to one. The bond length is increased to 149 pm. If only one electron is added
to an oxygen molecule, the superoxide ion, O2- results. The bond order is 1.5 and the
bond length is 128 pm.
The ionization of O2 to a cation causes a decrease in bond length to 112 pm. The electron
ionized is a π* antibonding electron and the bond order of O2+ is 2.5.

 Activity: Draw MO diagrams of F2 & Ne2 and account for properties of the same.

References:
1. Inorganic Chemistry: Principles of Structure & Reactivity by James E. Huheey, Ellen
A. Keiter & Riuchard L. Keiter
2. Inorganic Chemistry by Gary L. Miessler & Donald A. Tarr
3. Principles of Inorganic Chemistry by B.R. Puri, L.R. Sharma & K.C. Kalia