Molecular Orbital Theory:

Dr Mamta Bhardwaj
KEY WORD-Molecular orbitals,BMO,ABMO,Magnetic Nature-Diamagnetic and
paramagnetic
PRE READING MATERIAL

Orbital: An Orbital is a three dimensional space around nucleus where the probability of
finding an electron is high. They represent the probability of finding an electron in any one
place. They correspond to different energies. So an electron in an orbital has definite energy.
Each orbital is denoted by a number and a letter. The number denotes the energy level of the
electron in the orbital. Thus 1 refers to the energy level closest to the nucleus; 2 refers to the
next energy level further out, and so on. The letter refers to the shape of the orbital. The letters
go in the order s, p, d, f, g, h, i, j, etc.

Atomic Orbitals: Atomic orbitals are regions of space around the nucleus of an atom where
an electron is likely to be found. Atomic orbitals allow atoms to make covalent bonds. An
atomic orbital can have a maximum of two electrons. Atomic orbitals are labelled as s, p, d,
and f sublevels.

s Orbitals
The s orbital is spherical and hold a maximum of two electrons. It has one sub-energy level.
The order of size is 1s < 2s < 3s < …, as shown below.

.
p Orbitals:
The p orbital is dumbbell shaped and can hold up to six electrons. It has three sub energy
levels. These are given the symbols px, py and pz. The p orbitals at the second energy level
are called 2px, 2py and 2pz. There are similar orbitals at subsequent levels: 3px, 3py, 3pz,
4px, 4py, 4pz and so on.
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d ORBITALS
The d and f orbitals have more complex shapes. The d level has five sub-energy groups and
holds up to 10 electrons, The five 3d orbitals are called 3dxy, 3dxz, 3dyz, 3dx² - y², 3dz²

Molecular orbital (MO: Atoms join to form molecules. When two atoms move closer together
to form a molecule, atomic orbitals overlap and combine to become molecular orbitals.
Molecular orbitals are regions around molecules where electrons are most likely to be found.
The number of newly formed molecular orbitals is equal to the number of combined atomic
orbitals. The molecular orbital surrounds the two nuclei of the atoms, and electrons can move
around both nuclei. Similar to atomic orbitals, molecular orbitals maximally contain 2
electrons, which have opposite spins. Molecular orbitals are of two types, bonding molecular
orbitals and antibonding molecular orbitals. Bonding molecular orbitals contain electrons in
the ground state and antibonding molecular orbitals contain no electrons in the ground state.
Electrons may occupy in the antibonding orbitals if the molecule is in the excited state.
ENGINEERING CHEMISTRY

Differences between Atomic and Molecular Orbital

Atomic orbital Molecular orbital

Atomic orbital is the region having the Molecular orbital is the region having the
highest probability of finding an electron in highest probability of finding an electron of a
an atom molecule

Atomic orbitals are inherent property of an atom. Molecular orbitals are formed by combination of
atomic orbitals that have nearly the same energy
Formed by the electron cloud around the
atom

The shape is determined by the type of The shape is determined by the shapes of
atomic orbital(s,p,d or f) atomic orbitals that make the molecule. They
have complex shapes.

Schrodinger equation is used Linear combination of atomic orbitals

(LCAO) is used

Monocentric as it is found around a single Polycentric as it is found around different

reaction nuclei

Molecular Orbital Theory

Introduction:
Valence Bond Theory fails to answer certain questions like Why He2 molecule does not exist
and why O2 is paramagnetic Therefore in 1932 F. Hood and RS. Mulliken came up with theory
known as Molecular Orbital Theory to explain questions like above. According to Molecular
Orbital Theory individual atoms combine to form molecular orbitals, as the electrons of an
atom are present in various atomic orbitals and are associated with several nuclei.
Molecular orbital (MO) theory is a method for determining molecular structure in which
electrons are not assigned to individual bonds between atoms, but are treated as moving under
the influence of the nuclei in the whole molecule.

Postulates of MOT are:

• Two atoms come together, interact and forms a bond. All the atomic orbitals on either
nuclei mix together to form a new orbital called molecular orbital.
• The molecular orbitals are formed by mixing of the atomic orbitals of same energy
level and symmetry.
• After formation of molecular orbital, the atomic orbitals lose their identity.
• Each and every electron in the molecular orbital belongs to all the nuclei of the
molecules.
• Atoms have atomic orbitals with one nuclei and Molecules have molecular orbitals
with n nuclei. Thus, atoms are monocentric while molecules are polycentric.
• The number of molecular orbitals formed is equal to the atomic orbitals mixing.
• Molecular orbitals can be bonding, anti-bonding, and non-bonding orbitals.
Bonding molecular orbitals are lower in energy than the corresponding anti-bonding
orbitals.
ENGINEERING CHEMISTRY

• Each molecular orbital is described by a wave function Ψ, which in turn is associated

with a set of quantum number.
• Electrons fill up these orbitals in the same way as atomic orbitals in accordance to the
3 principles (Aufbau, Hunds and Pauli Principle).
• The Aufbau principle states that orbitals are filled with the lowest energy first.
• The Pauli exclusion principle states that the maximum number of electrons occupying
an orbital is two, with opposite spins.
• Hund’s rule states that when there are several MOs with equal energy, the electrons
occupy the MOs one at a time before two occupy the same MO.
Electrons may be considered either of particle or of wave nature. Therefore, an electron in an
atom may be described as occupying an atomic orbital, or by a wave function Ψ, which are
solution to the Schrodinger wave equation. Wave function is a mathematical function related
to probability of finding the particle in a particular region of space.
Electrons in a molecule are said to occupy molecular orbitals. The wave function of a
molecular orbital may be obtained by one of two methods:
1. Linear Combination of Atomic Orbitals (LCAO).
2. United Atom Method.
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 molecule. Consider two atoms A and B
which have atomic orbitals described by the wave functions ΨA and ΨB .If electron cloud of
these two atoms overlap, then the wave function for the molecule can be obtained by a
linear combination of the atomic orbitals ΨA and ΨB i.e. by subtraction or addition of wave
functions of atomic orbitals
ΨMO= ΨA + ΨB
The above equation forms two molecular orbitals
Bonding Molecular Orbitals
When addition of wave function takes place, the type of molecular orbitals formed are called
Bonding Molecular orbitals and is represented by ΨMO = ΨA + ΨB.
They have lower energy than atomic orbitals involved. It is similar to constructive interference
occurring in phase because of which electron probability density increases resulting in
formation of bonding orbital. Molecular orbital formed by addition of overlapping of two s
orbitals shown in Figure 1. It is represented by s.

Anti-Bonding Molecular Orbitals

When molecular orbital is formed by subtraction of wave function, the type of molecular
orbitals formed are called Antibonding Molecular Orbitals and is represented by ΨMO = ΨA -
ΨB.
They have higher energy than atomic orbitals. It is similar to destructive interference
occurring out of phase resulting in formation of antibonding orbitals. Molecular Orbital formed
by subtraction of overlapping of two s orbitals are shown in figure no. 2. It is represented by
σ* (*) is used to represent antibonding molecular orbital) called Sigma Antibonding.
ENGINEERING CHEMISTRY

Fig. 1 Formation of Bonding and Anti-Bonding Orbital

Therefore, Combination of two atomic orbitals results in formation of two molecular orbitals,
bonding molecular orbital (BMO) whereas other is anti-bonding molecular orbital (ABMO).
BMO has lower energy and hence greater stability than ABMO. First BMO are filled then
ABMO starts filling because BMO has lower energy than that of ABMO.
Formation of molecular orbitals occurs by the combination of atomic orbitals of proportional
symmetry and comparable energy. Therefore, a molecular orbital is polycentric and atomic
orbital is monocentric. Number of molecular orbitals formed is equal to the number of atomic
orbitals.

Relative Energies of Molecular Orbitals

Bonding Molecular Orbitals (BMO) - Energy of Bonding Molecular Orbitals is less than that
of Anti Bonding Molecular Orbitals because the attraction of both the nuclei for both the
electron (of the combining atom) is increased.
Anti-Bonding Molecular Orbitals (ABMO) - Energy of Anti Bonding Molecular Orbitals is
higher than Bonding Molecular Orbitals because the electrons move away from the nuclei and
are in repulsive state.
The Energies of Bonding Molecular Orbitals and Anti-Bonding Molecular Orbitals are shown
in
Fig 2 :
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Molecular orbitals of diatomic molecules:

Molecular Orbitals for diatomic Molecules formed from a Linear Combination of Atomic
Orbitals is shown below:

Filling Electrons in MO Diagrams

The next step in constructing an MO diagram is filling the newly formed molecular orbitals
with electrons. Three general rules apply:
• The Aufbau principle states that orbitals are filled starting with the lowest energy
• The Pauli exclusion principle states that the maximum number of electrons. occupying
an orbital is two, with opposite spins.
• Hund’s rule states that when there are several MOs with equal energy, and the
electrons occupy the MOs one at a time before two occupy the same MO.

The filled MO that is highest in energy is called the Highest Occupied Molecular Orbital, or
HOMO; the empty MO just above it is the Lowest Unoccupied Molecular Orbital, or LUMO.
The electrons in the bonding MOs are called bonding electrons, and any electrons in the
antibonding orbital are called antibonding electrons. The reduction these electrons’ energy is
the driving force for chemical bond formation.
ENGINEERING CHEMISTRY

Energy Level Diagram

The factors upon which relative energies of molecular orbitals depend are:
(i) Energies of the Atomic orbitals combining to form Molecular Orbitals.
(ii) The extent of overlapping between the atomic orbitals. The greater the overlap, the more
the bonding orbital is lowered and the anti-bonding orbital is raised in energy relative to AOs
1s Atomic Orbitals (AOs) of two atoms form two Molecular Orbitals (MOs) designated as
s1s and s *1s.The 2s and 2p orbitals (eight AOs of two atoms) form four bonding MOs and
four anti-bonding MOs as:
Bonding MOs: σ 2s, σ 2pz, π 2px, π 2py
Anti – Bonding MO: σ *2s, σ *2pz, π *2px, π *2py
The order of increasing energy of molecular orbitals obtained by combination of 1s, 2s and
2p orbitals of two atoms is →
σ1s, σ *1s, σ 2s, σ *2s, σ 2pz, π 2px = π 2py, π *2px= π *2py, σ *2pz
(Energy Increases from left to right)

Bond order:
It may be defined as the half of difference between the number of electrons present in the
bonding orbitals and the antibonding orbitals that is,
Bond order (B.O.) = (No. of electrons in BMO - No. of electrons in ABMO)/ 2
Those with positive bonding order are considered stable molecule while those with negative
bond order or zero bond order are unstable molecule.

Magnetic Behavior: If all the molecular orbitals in species are spin paired, the substance is
diamagnetic. But if one or more molecular orbitals are singly occupied it is paramagnetic.

Molecular orbital energy level diagram of Nitrogen molecule (N2)

The electronic configuration of nitrogen atom is 1s2 2s2 2p 1x 2 1y 2p 1z and N molecule
2 has 14
electrons. The Molecular orbital diagram is shown in Fig. 3
The molecular orbital electronic configuration of the molecule is:

N2: KK (σ2s)2 < (σ*2s)2 < (Л 2px)2=(Л2py)2 < (σ2pz)2

8−2
Bond Order= =3
2
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Fig 3: Molecular orbital energy level diagram of N2 molecule

Thus, nitrogen molecule has three bonds, one σ and two π-bonds. This is in accordance with
very high bond dissociation energy (945 kJ mol-1) and small bond length (110 pm) of the
molecule. The molecule has no unpaired electrons and therefore it is diamagnetic.
Molecular orbital energy level diagram of Oxygen molecule (O2)
Oxygen atom has electronic configuration of is 1s2 2s1 2px22y 12pz Therefore, oxygen
molecule has 16 electrons. In the formation of molecular orbitals, the electrons in the inner
shells are expressed as KK denoting (σ1s) 2(σ*1s) 2. The remaining 12 electrons are filled in
molecular orbitals as shown in figure 4
For O2
σ1s, σ *1s, σ 2s, σ *2s, σ 2pz, [π2px = π2py], [π*2px= π*2py], σ *2pz
The electronic configuration of the molecule is

O2 : KK (σ2s)2 < (σ*2s)2 < (σ2pz)2 < (Л 2px)2=(Л2py)2 < (Л*2px)1= (Л*2py)1
8−4
Bond Order= =2
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Fig 4: Molecular orbital energy level diagram of O2

Thus, oxygen molecule has two bonds one σ and one π Further, in
accordance with Hund’s rule, the last two electrons in π*2px and π*2py
orbitals will remain unpaired. Therefore, the molecule has paramagnetic
character due to the presence of two unpaired electrons. These facts are in
accordance with experimental observations. The bond dissociation
energy in O2 molecule is 498 kJ mol-1and bond length is 121 pm.

Metallic Bonding:
The force that hold the atoms of pure metal together in a crystal as a result
of the attraction between positive ions and surrounding freely mobile
delocalized electrons is known as metallic bond.
 Application: Computational Chemistry in Drug
Design
While the descriptions of bonding described in this chapter involve many theoretical concepts,
they also have many practical, real-world applications. For example, drug design is an
important field that uses our understanding of chemical bonding to develop pharmaceuticals.
This interdisciplinary area of study uses biology (understanding diseases and how they operate)
to identify specific targets, such as a binding site that is involved in a disease pathway. By
modeling the structures of the binding site and potential drugs, computational chemists can
predict which structures can fit together and how effectively they will bind
(Figure 6.9.66.9.6). Thousands of potential candidates can be narrowed down to a few of the
most promising candidates. These candidate molecules are then carefully tested to determine
side effects, how effectively they can be transported through the body, and other factors.
Dozens of important new pharmaceuticals have been discovered with the aid of computational
chemistry, and new research projects are underway.

QUESTIONS BASED ON MOLECULAR ORBITAL THEORY

SECTION-01
This set of Engineering Chemistry Multiple Choice Questions & Answers (MCQs)
focuses on “Molecular Orbital Theory”.(Q 1 TO 10)

1. If the sign of the wave function is unchanged when the orbital is reflected about its
centre, the orbital is ______________
a) Gerade
b) Ungerade
c) Gerade as well as Ungerade
d) None of the mentioned
2. The filling of molecular orbital takes place according to __________
a) The Aufbau Principle
b) Pauli Exclusion Principle
c) Hund’s rule of maximum multiplicity
d) All of the mentioned

3. Bond Order of O2, F2, N2 respectively are __________

a) +1, +2, +3
b) +2, +3, +1
c) +2, +1, +3
d) +3, +2, +1

4. Arrange the following molecules in decreasing bond length.

a) O2 > O2– > O2+ > O22-
b) O22- > O2– > O2 > O2+
c) O22- > O2– > O2+ > O2
d) O2– > O2+ > O22- > O2

5. Arrange the following molecules in the order of increasing stability.

a) N2+ < N2 < N2– < N22-
b) N22- < N2– < N2 < N2+
c) N22- < N2– = N2+ < N2
d) N2 < N2+ = N2– < N22-

6. On the basis of molecular orbital theory, select the most appropriate option.
a) The bond order of O2 is 2.5 and it is paramagnetic
b) The bond order of O2 is 1.5 and it is paramagnetic
c) The bond order of O2 is 2 and it is diamagnetic
d) The bond order of O2 is 2 and it is paramagnetic

7. Which of the following molecule does not exist due to its zero bond order?
a) H2+
b) He2+
c) He2
d) H2–

8. The relative energies of molecular orbitals in increasing order have been found to be
as follows.
(σ1s) < (σ*1s) < (σ2s) < (σ*2s) < [(π2py)(π2pz)] < (σ 2px) < [(π*2py)(π*2pz)] < (σ*2px)
a) For O2 to Ne2
b) For H2 to N2
c) For H2 to Ne2
d) For N2 to Ne2

9. According to Molecular Orbital Theory, the shape and size of a molecular orbital
depends upon _________
a) Shape and size of the combining atomic orbitals
b) Numbers of the combining atomic orbitals
c) Orientation of the combining atomic orbitals
d) All of the mentioned
10. Choose the incorrect statement from the following options.
a) In bonding molecular orbital, electron density is low in the region between the nuclei
of bonded atoms
b) The energy of antibonding molecular orbital is higher than that of atomic orbitals from
which it is formed
c) Every electron in bonding molecular orbital contributes toward stability of the molecule
d) Antibonding takes place when lobes of atomic orbitals have different signs

SECTION -02

Q.11.Calculate the bond order of He2+ and O2-2 .

Q.12 What is bond order? Calculate the bond order of O 2 .

Q.13. On the basis of molecular orbital theory ,prove that the molecule of oxygen is
paramagnetic in nature.

Q.14. Draw molecular orbital diagrams and calculate bond order for N2 and CO.

Q.15.With the help of molecular orbital diagram explain why hydrogen forms diatomic
molecule while helium remains monoatomic.

Q.16. With the help of molecular orbital diagram arrange the following molecule/ion in
order of their increasing bond length O2.O2_ and O2+.

Q.17. With the help of molecular orbital theory explain the paramagnetic character of
oxygen and diamagnetic character of nitrogen .

Q.18. Calculate the bond order of N2-, CO,NO and O2-.

Q.19 With the help of molecular orbital diagram of NO molecule.

Q.20. Account for paramagnetic behaviour of oxygen on the basis of molecular orbital
theory.

Q.21.Compare the bond energy,bond length and magnetic character of CN and CN -

species with the help of molecular orbital theory.

Q.22. Of the following species,which has the shortest bond length: NO,NO +,NO++,NO-.

Q.23.Explain the molecular orbital theory with example of oxygen.

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