CHEMICAL BONDING AND MOLECULAR STRUCTURE-II

Quantum Theory of Covalent Bond.

• Atoms combine to acquire stability.

• Maximum stability is attained when they acquire minimum energy.

• When two atoms are far apart, there is no attraction or repulsion between the atoms.
Total energy is the sum of energies of the two atoms and no bond formation takes place.
• As atoms come closer, three types forces come into action between the atoms.
1. Nucleus – Electron Attraction
2. Electron – Electron Repulsion
3. Nucleus- Nucleus Repulsion
• In the beginning attractive forces dominate repulsive forces. This results in decrease
of potential energy.
• When atoms come closer and closer, attractive force increases continuously and
potential energy also decreases.
• At a certain internuclear distance, the attractive force becomes maximum and the
potential energy of the system becomes minimum. At this state the two atoms
combine to form covalent bond.
• The internuclear distance corresponding to this state is called bond length and the
energy corresponding to this state is called bond energy.
• If atoms are brought further closer, the repulsive forces dominate and potential energy
of the system increases rapidly.

• There are two theories of formation of covalent bond.

1. Valence Bond theory (VBT)
2. Molecular Orbital theory (MOT)
 VALENCE BOND THEORY (VBT)

This theory was suggested by Heitler and London and was later developed by Pauling and
Slater.

Postulates of Valence Bond Theory.

1. A covalent bond is formed by the mutual overlapping of atomic orbitals containing

unpaired electrons of opposite spin.
2. The strength of a covalent bond depends on the extent of overlapping of the two
atomic orbitals. Higher the overlap greater is the strength of the covalent bond.
3. Atomic orbitals of only unpaired electrons take part in overlapping. The atomic
orbitals of other electrons do not overlap.
4. If an atom possesses more than one atomic orbital containing unpaired electrons
multiple bonds may be formed.
5. Combining atoms and atomic orbitals retain their identity in the molecule formed by
their combination.
6. The covalent bond formed lies in the direction of their maximum overlapping. Covalent
bonds are thus directional in nature.
7. An axial overlap between two atomic orbitals always forms a stronger bond known as
Sigma(𝜎) bond.
8. A parallel overlap between two atomic orbitals (p- orbitals) form a weaker bond
known as pi (𝜋) bond.
9. Between two orbitals of same energy, more directionally concentrated orbitals form
a stronger bond. Thus, dumbbell shaped p-orbitals form a stronger bond as compared
to spherically symmetrical s-orbitals.

Types of orbital overlapping.

1. s-s overlapping.
Two s- orbitals always overlap axially. Therefore, overlapping of two s-orbital always
forms sigma bond.
Example: H2 molecule

2. s-p overlapping.
Overlapping of s and p orbitals always takes place axially and therefore, forms a sigma
bond.
Example: H-F, HCl, HBr, HI
 3. p-p overlapping.
p-p overlapping can take place in two ways.
i) Axial Overlapping / end to end overlapping / head on overlapping.
When two p-orbitals overlap axially, a sigma bond is formed.

Example : F2, Cl2, Br2, I2

ii) Parallel Overlapping / side wise overlapping / lateral overlapping.

Parallel overlapping of two p-orbitals gives a pi-bond. A pi bond consists of
two electron clouds or charge clouds, one above and one below the plane.
Examples: O2, N2
O2 molecule

N2 molecule

Comparison of Sigma(𝝈) and pi(𝝅) bonds.

Sigma(𝝈) bonds pi(𝝅) bonds

1. Sigma bonds are formed by the axial pi bonds are formed by the parallel
overlapping of half-filled atomic orbitals overlapping of half-filled p-orbitals

2. Electron cloud is symmetrical Pi bond consists two electron clouds, one

above and one below the axial line.
3. Sigma bond has no nodal plane. Pi bond has nodal plane along the inter
nuclear axis.
4. Sigma bonds are strong and less reactive. Pi bonds are weak and more reactive.

5. Sigma electrons are localized. Pi electrons are delocalized.

 6. Sigma bond can have independent existence. Pi bond always exists along with sigma
bond.
7. Number of sigma bonds decides the geometry Pi bonds do not affect the geometry of the
of the molecule. molecule.

8. Free rotation of atoms or groups about sigma Free rotation is not possible. (Free rotation
bond is possible. is restricted.)

Explanation of valency of Be, B and C.

Elements Electronic configuration No. of half-filled Expected Actual

orbitals valency valency
Beryllium 1s2,2s2 0 0 2
Boron 1s2,2s2,2px1 1 1 3
Carbon 1s2,2s2,2px1, 2py1 2 2 4

Explanation.

Be acquires two half-filled orbitals by the excitation of one electron from 2s orbital to 2px
orbital as follows. Be* - 1s2,2s1,2px1.

Now, there are two half-filled orbitals and Be can exhibit covalency equal to 2.

B acquires three half-filled orbitals by the excitation of one electron from 2s orbital to 2py
orbital as follows. B* - 1s2,2s1,2px1 2py1.

Now, there are three half-filled orbitals and B can exhibit covalency equal to 3.

C acquires four half-filled orbitals by the excitation of one electron from 2s orbital to 2pz orbital
as follows. C* - 1s2,2s1,2px1 2py1, 2pz1.

Now, there are four half-filled orbitals and C can exhibit covalency equal to 4.

HYBRIDISATION
In order to explain the geometry of molecules, identical bond lengths and identical bond
angles, Linus Pauling introduced a hypothetical concept of hybridization

Definition: Hybridisation is the intermixing of atomic orbitals of comparable energies and

different shapes to form equal number of new orbitals (called hybrid orbitals) of identical
shape, equal energy and definite orientation in space.

Rules of Hybridisation.

1. Atomic orbitals of a single atom can only take part in hybridization.

2. Atomic orbitals taking part in hybridization should be of comparable energies.
 3. Number of hybrid orbitals formed is equal to the number of atomic orbitals taking part
in hybridization.
4. It is the atomic orbital that undergoes hybridization not the electrons
5. Hybrid orbitals have some preferred directions
6. Hybrid orbitals form only sigma bonds.

Types of Hybridisation

1. sp3 hybridisation.
It is the intermixing of one s-orbital and three p-orbitals to form four hybrid orbitals
which are directed to the four corners of a regular tetrahedron at an angle of 109o28’.

Example 1. Methane. (CH4)

Electronic configuration of carbon in the ground state is :

C (ground state) ⥮ ⥮ ↿ ↿
1s2 2s2 2px1, 2py1. 2pz0.

Electronic configuration of carbon in the excited state is:

C* (excited state) ⥮ ↿ ↿ ↿ ↿
1s2 2s1 2px1, 2py1. 2pz1.

sp3 hybridisation

2s,2px, 2py and 2pz orbitals of carbon atom undergo sp3 hybridisation to form four hybrid
orbitals of equal energy and identical shape. The hybrid orbitals are directed to the four
corners of a regular tetrahedron at 109028’.

C (hybrid state) ⥮ ↿ ↿ ↿ ↿

Each hybrid orbital containing unpaired electron overlaps with 1s orbital of hydrogen atom
to form four C-H sigma bonds. Thus, the resulting methane molecule is tetrahedral in shape
with H-C-H bond angle equal to 109028’.
Example 2. Ethane (CH3-CH3)

Electronic configuration of carbon in the ground state is :

C (ground state) ⥮ ⥮ ↿ ↿
1s2 2s2 2px1, 2py1. 2pz0.

Electronic configuration of carbon in the excited state is:

C* (excited state) ⥮ ↿ ↿ ↿ ↿
1s2 2s1 2px1, 2py1. 2pz1.

sp3 hybridisation

In ethane, both carbon atoms undergo sp3 hybridisation separately. The hybrid orbitals are
directed to the four corners of a regular tetrahedron at 109028’. One hybrid orbital of one
carbon atom overlaps axially with a hybrid orbital of the other carbon atom to form a C-C
sigma bond. The remaining three hybrid orbitals of each carbon atom overlap with 1s orbital
of hydrogen atoms to form six C-H sigma bonds. Thus ethane molecule contains one C-C
sigma bond and six C-H sigma bonds.

Note:

• Each sp3 hybrid orbital has 25% s-character and 75% p-character.
• In alkanes C- atoms are sp3 hybridised.
• More examples: CCl4, SiCl4, NH4+, H2SO4 etc.

2. sp2 Hybridisation
It is the intermixing of one s-orbital and two p-orbitals to form three hybrid orbitals which are
directed to the three corners of an equilateral triangle at an angle of 1200.
Example 1. Boron trifluoride. (BF3)

Electronic configuration of boron in the ground state is:

B (ground state) ⥮ ⥮ ↿
1s2 2s2 2px1, 2py0. 2pz0.

Electronic configuration of boron in the excited state is:

B* (excited state) ⥮ ↿ ↿ ↿
1s2 2s1 2px1, 2py1. 2pzo.

sp2 hybridisation

2s,2px, and 2py orbitals of boron atom undergo sp2 hybridisation to form three hybrid orbitals
of equal energy and identical shape. The hybrid orbitals are directed to the three corners of
an equilateral triangle at an angle of 1200.

B (hybrid state) ⥮ ↿ ↿ ↿

Each hybrid orbital containing unpaired electron overlaps with 2pz orbital of fluorine atom to
form three B-F sigma bonds. Thus, the resulting BF3 molecule has a trigonal planar
geometry with F-B-F bond angle equal to 1200

Example 2. Ethene or Ethylene or (CH2=CH2)

Electronic configuration of carbon in the ground state is :

C (ground state) ⥮ ⥮ ↿ ↿
1s2 2s2 2px1, 2py1. 2pz0.

Electronic configuration of carbon in the excited state is:

C* (excited state) ⥮ ↿ ↿ ↿ ↿
1s2 2s1 2px1, 2py1. 2pz1.

sp2 hybridisation

In ethene, both carbon atoms undergo sp2 hybridisation separately. The hybrid orbitals are
directed to the three corners of an equilateral triangle at an angle of 1200. The unhybridized
2pz orbital of each carbon atom lies perpendicular to the plane of the hybrid orbitals. One
hybrid orbital of one carbon atom overlaps axially with a hybrid orbital of the other carbon
atom to form a C-C sigma bond. The remaining two hybrid orbitals of each carbon atom
overlap with 1s orbital of hydrogen atoms to form four C-H sigma bonds. The unhybridized 2pz
orbitals undergo parallel overlap to form a C-C pi bond. Thus, ethene molecule has a planar
geometry and it contains five sigma bonds and a pi bond. The H-C-H bond angle is 117.50 and
H-C-C bond angle is 1210.

Note:

• Each sp2 hybrid orbital has 33.33% s-character and 66.67% p-character.
• In alkenes double bonded C- atoms are sp2 hybridised.
• More examples: BCl3, NO3-, CO32- etc.

3. sp hybridisation.
It is the intermixing of one s-orbital and one p-orbital to form two hybrid orbitals which are
arranged linearly at an angle of 1800.

Example 1. Beryllium fluoride. (BeF2)

Electronic configuration of beryllium in the ground state is:

Be (ground state) ⥮ ⥮
1s2 2s2 2px1, 2py0. 2pz0.

Electronic configuration of beryllium in the excited state is:

Be* (excited state) ⥮ ↿ ↿

1s2 2s1 2px1, 2py . 2pzo.

sp hybridisation
2s,and 2px, orbitals of boron atom undergo sp hybridisation to form two hybrid orbitals of
equal energy and identical shape. The hybrid orbitals are arranged linearly at an angle of 1800.

Be (hybrid state) ⥮ ↿ ↿

Each hybrid orbital containing unpaired electron overlaps with 2pz orbital of fluorine atom to
form two Be-F sigma bonds. Thus, the resulting BeF2 molecule has a linear geometry with
F-Be-F bond angle equal to 1800.

Example 2. Ethyne or Acetylene or (CH≡CH)

Electronic configuration of carbon in the ground state is :

C (ground state) ⥮ ⥮ ↿ ↿
1s2 2s2 2px1, 2py1. 2pz0.

Electronic configuration of carbon in the excited state is:

C* (excited state) ⥮ ↿ ↿ ↿ ↿
1s2 2s1 2px1, 2py1. 2pz1.

sp hybridisation

In ethyne, both carbon atoms undergo sp hybridisation separately. The hybrid orbitals are
arranged linearly at an angle of 1800. The unhybridized 2py and 2pz orbitals of each carbon
atom are perpendicular to each other and lies perpendicular to the plane of the hybrid
orbitals. One hybrid orbital of one carbon atom overlaps axially with a hybrid orbital of the
other carbon atom to form a C-C sigma bond. The remaining one hybrid orbital of each
carbon atom overlap with 1s orbital of hydrogen atoms to form two C-H sigma bonds. The
unhybridized 2py and 2pz orbitals undergo parallel overlap to form two C-C pi bonds. Thus,
ethyne molecule has a linear geometry with H-C-C bond angle equal to 1800. Acetylene
molecule contains three sigma bonds and two pi- bonds.
Note:

• Each sp hybrid orbital has 50% s-character and 50% p-character.

• In alkynes triple bonded C- atoms are sp hybridised.
• More examples: CO2, CS2, HgCl2, ZnCl2 etc.

Hybridisation Involving d-orbitals

sp3d hybridisation.

It is the intermixing of one s-orbital, three p-orbitals and one d-orbital to form five hybrid
orbitals which are directed to the five corners of a trigonal bipyramid.

• Three hybrid orbitals are directed to the three corners of an equilateral triangle at angle
of 1200.
• The remaining two hybrid orbitals lie perpendicular to the plane of triangle lying above
and below it.
• Examples: PF5, PCl5 etc.

Structure of PCl5

Outer electronic configuration of phosphorus in the ground state is:

P (ground state) ⥮ ↿ ↿ ↿

3s2 3px1, 3py1. 3pz1. 3d

Outer Electronic configuration of phosphorus in the excited state is:

P* (excited state) ↿ ↿ ↿ ↿ ↿

3s1 2px1, 2py1. 2pz1. 3d1

sp3d hybridisation

3s,3px, 3py, 3pz and one 3d orbitals of phosphorus atom undergo sp3d hybridisation to form
five hybrid orbitals which are directed to the five corners of a trigonal bipyramid. These hybrid
orbitals overlap with 3pz orbitals of chlorine atoms to form five P-Cl sigma bonds. Thus, PCl5
has a trigonal bipyramidal geometry.

Three P-Cl bonds lie in one plane at an angle of 1200 to one another. These bonds are
called equatorial bonds. The remaining two P-Cl bonds lie perpendicular to the plane
containing equatorial bonds making an angle 900 with the plane. These bonds are called axial
bonds.

Note.

• Axial P-Cl bonds are longer than equatorial P-Cl bonds.

• Axial P-Cl bond pairs experience greater repulsion from other bond pairs. Hence the
bond length increases slightly.
• Axial bonds are weaker than equatorial bonds. Therefore, PCl5 is highly reactive.
• Due to different bond lengths and bond angles, it has an irregular geometry.
• Though it has an irregular geometry, net dipole moment of the molecule is zero.
Hence, it is a non-polar molecule.

sp3d2 hybridisation.

It is the intermixing of one s-orbital, three p-orbitals and two d-orbitals to form six hybrid
orbitals which are directed to the six corners of an octahedron (square bipyramid) at an
angle of 900.
Example: SF6

Outer electronic configuration of Sulphur in the ground state is:

S (ground state) ⥮ ⥮ ↿ ↿

3s2 3px2, 3py1. 3pz1. 3d

Outer Electronic configuration of Sulphur in the second excited state is:

S* (second excited state) ↿ ↿ ↿ ↿ ↿ ↿

3s1 2px1, 2py1. 2pz1. 3d1 3d1

sp3d2 hybridisation

3s,3px, 3py, 3pz and two 3d orbitals of Sulphur atom undergo sp3d2 hybridisation to form six
hybrid orbitals which are directed to the six corners of an octahedron (square bipyramid) at
an angle of 900. These hybrid orbitals overlap with 2pz orbitals of fluorine atoms to form six
S-F sigma bonds. Thus, SF6 has an octahedral geometry with F-S-F bond angle equal to 900.
sp3d3 hybridisation.

It is the intermixing of one s-orbital, three p-orbitals and three d-orbital to form seven hybrid
orbitals which are directed to the seven corners of a pentagonal bipyramid.

• Five hybrid orbitals are directed to the five corners of a regular pentagon at angle of 720.
• The remaining two hybrid orbitals lie perpendicular to the plane of pentagon lying above
and below it.
• Example: IF7

Structure of IF7

Outer electronic configuration of iodine in the ground state is:

I (ground state) ⥮ ⥮ ⥮ ↿

5s2 5px2, 3py2. 5pz1. 5d

Outer Electronic configuration of iodine in the third excited state is:

I* (third excited state) ↿ ↿ ↿ ↿ ↿ ↿ ↿

5s1 5px1, 5py1. 5pz1. 5d1 5d1 5d1

sp3d3 hybridisation

5s,5px, 5py, 5pz and three 5d orbitals of iodine atom undergo sp3d3 hybridisation to form seven
hybrid orbitals which are directed to the seven corners of a pentagonal bipyramid. These
hybrid orbitals overlap with 2pz orbitals of fluorine atoms to form seven I-F sigma bonds. Thus,
IF7 has a pentagonal bipyramidal geometry.

• Five I-F bonds lie in one plane at an angle of 720 to one another. These bonds are called
equatorial bonds.
• The remaining two I-F bonds lie perpendicular to the plane containing equatorial
bonds making an angle 900 with the plane. These bonds are called axial bonds.
• Axial I-F bonds(179pm) are shorter than equatorial I-F bonds(186pm).
• Equatorial I-F bond pairs experience greater repulsion from other bond pairs d. Hence
the bond length increases slightly.
• Due to different bond lengths and bond angles, it has an irregular geometry.
• Though, it has an irregular geometry, net dipole moment of the molecule is almost
zero. Hence, it is a non-polar molecule.
VALENCE SHELL ELECTRON PAIR REPULSION THEORY. [VSEPR Theory] [Sidgwick and Powell]

In 1940, Sidgwick and Powell suggested a basic theory based on the repulsive interactions of
electron pairs in the valence shell of atoms. This theory gives a simple method for predicting
the shapes of covalent compounds.

Postulates of VSEPR Theory

1. The geometry or shape of a molecule depends upon the number of valence shell
electron pairs present around the central atom
2. Electron pairs in the valence shell repel one another and try to stay as far apart as
possible to acquire a state of maximum stability or minimum repulsion or minimum
energy
3. Repulsion between lone pair and lone pair, lone pair and bond pair and bond pair and
bond pair are different and follows the order:
Lone pair(lp) – lone pair(lp) > lone pair(lp) – bond pair(bp) > bond pair (bp)– bond pair(bp).
4. Repulsive forces decrease sharply with the increase in angles between the electron
pairs. They are strong at 90° weaker at 120° and weakest at 180°.
5. Presence of lone pair of electron causes distortion in the geometry of the molecule.

Prediction of geometrical shapes using VSEPR theory

A. Molecules Containing Bond Pairs Only

Example 1 . BeF2

In BeF2, the central Be atom possesses two bond pairs of electrons and no lone pairs. For
maximum stability, these electron pairs will be arranged at an angle of 1800. Thus, BeF2 has
a linear geometry.

Example 2. BF3

In BF3, the central B atom possesses three bond pairs of electrons and no lone pairs. For
maximum stability, these electron pairs will be arranged at an angle of 1200. Thus, BF3 has a
trigonal planar geometry.

Example 3. CH4

In CH4, the central C atom possesses four bond pairs of electrons and no lone pairs. For
maximum stability, these electron pairs will be arranged at an angle of 109028’. Thus, CH4 has
a tetrahedral geometry.
B. Molecules Containing Bond Pairs and Lone pairs.

Example 1. Ammonia – NH3

Electronic configuration of nitrogen is 1s22s22px12py12pz1. Nitrogen atom of ammonia is sp3

hybridised. 2s,2px,2py and 2pz orbital undergo sp3 hybridisation to form four hybrid orbitals.
One of the hybrid orbitals contains a pair of electrons. Hybrid orbitals containing unpaired
electrons overlap with 1s orbitals of hydrogen atom to form three N-H sigma bonds.

Thus, valence shell of nitrogen atom of ammonia contains three bond pairs and one lone pair.
According to VSEPR theory, lone pair-bond pair repulsion is stronger than bond pair-bond
pair repulsion. Thus, lone pairs will repel the bond pairs strongly and bond angle decreases
to 1070 from the expected angle of 109028’. Ammonia molecule has a trigonal pyramidal
geometry.

Example 2. Water– H2O

Electronic configuration of oxygen is 1s22s22px22py12pz1. Oxygen atom of water is sp3

hybridised. 2s,2px,2py and 2pz orbital undergo sp3 hybridisation to form four hybrid orbitals.
Two hybrid orbitals contain paired electrons. Hybrid orbitals containing unpaired electrons
overlap with 1s orbitals of hydrogen atom to form two O-H sigma bonds.

Thus, valence shell of oxygen atom of water contains two bond pairs and two lone pairs.
According to VSEPR theory, lone pair - lone pair repulsion > lone pair-bond pair repulsion >
bond pair-bond pair repulsion. Thus, the two lone pairs will repel the bond pairs strongly and
bond angle decreases to 104.50 from the expected angle of 109028’. Water molecule has a
bent or angular geometry (V -shape).
Prediction of Hybridisation.

The type of hybridization can be predicted by the following general formula.

N = ½ [V + M – C + A]

Where, N = Number electron pairs (bond pairs + lone pairs) or number of hybrid orbitals.

V = Number of valence electrons. M = Number of monovalent atoms

C = Charge number of cation A = Charge number of anion.

N 2 3 4 5 6 7
Hybridisation sp sp2 sp3 sp3d sp3d2 sp3d3

Question. Predict the hybridization of the central atom in the following molecules or ions.

CO2, SO2, SO3, H2SO4, HNO3, H3PO4, HClO4, HClO3, HClO2, H2CO3, SiCl4, ClF3, IF5, XeF2, XeF4,
XeF6, COCl2, NH4+, POCl3, SO42-, ClO4-, PO43-

Number of Electron Pairs and Geometry of molecules

Number hybridisation Number Number General Geometry Examples

of of bond of lone formula
electron pairs pairs (L)
pairs
2 sp 2 0 AX2 linear BeF2, CO2
3 sp2 3 0 AX3 Trigonal planar BF3, BCl3, CO32-,
NO3-
3 sp2 2 1 AX2L Angular SO2
4 sp3 4 0 AX4 tetrahedral CH4,CCl4,SiCl4,
NH4+
4 sp3 3 1 AX3L pyramidal NH3,
PH3,NF3,NCl3,PCl3
4 sp3 2 2 AX2L2 angular H2O, H2S
5 sp3d 5 0 AX5 Trigonal PCl5, PF5
bipyramidal
5 sp3d 4 1 AX4L See-Saw shape SF4
5 sp3d 3 2 AX3L2 T-shape ClF3, ICl3
5 sp3d 2 3 AX2L3 linear XeF2, I3-
6 sp3d2 6 0 AX6 octahedral SF6
6 sp3d2 5 1 AX5L Square ClF5, BrF5
pyramidal
6 sp3d2 4 2 AX4L2 Square planar XeF4
7 sp3d3 7 0 AX7 Pentagonal IF7
bipyramidal
 Drawbacks Of Valence Bond Theory.

1. Unable to explain the formation of coordinate bond.

2. Unable to explain the paramagnetic character of oxygen molecule.

3. Unable to explain bonding in metals and odd electron molecules.

MOLECULAR ORBITAL THEORY or M.O. THEORY [Friedrich Hund- Robert Mulliken]

Postulates of M.O. Theory.

1. When two atoms approach each other, their atomic orbitals lose their identity and mutually
overlap to form new orbitals called molecular orbitals.

2. Molecular orbitals are polycentric. They surround the nuclei of the combining atoms instead
of moving around a particular nucleus.

3. Molecular orbitals are formed by the combination of atomic orbitals of comparable energies
and proper orientation.

4. Number of molecular orbitals formed is same as the number of combining atomic orbitals.

5. Molecular orbitals can accommodate a maximum of two electrons.

6. Like atomic orbitals, molecular orbitals also obey Pauli's Exclusion Principle, Hund's Rule of
maximum multiplicity and Aufbau Principle.

7. Shapes molecular orbitals depends on the shapes of combining atomic orbitals.

Difference Between Atomic Orbital and Molecular Orbital

Atomic Orbital Molecular Orbital

1. Atomic orbitals are monocentric. ie. Electrons Molecular orbitals are polycentric. ie electrons
in atomic orbital are under the influence of only on molecular orbital are under the influence of
one nucleus. two or more nuclei.

2. Atomic orbitals are inherent property of Molecular orbitals are formed by the
atoms. These are obtained by solving combination of atomic orbitals.
Schrodinger wave equation.

3. Atomic orbitals possess higher energy and are Molecular orbitals possess lower energy and are
less stable. more stable.
4. They have simple shapes. They have complex shapes.

5. Atomic orbitals are designated as s,p,d,f etc . Molecular are designated as 𝝈 , 𝝈∗ , 𝝅, 𝝅∗ etc.
Types of Molecular Orbitals.

When two combining atoms approach each other, the electron waves of the atoms can
combine in two ways:

1. If the two electron waves are in phase, the electron waves get added up (constructive
interference of waves). The resulting wave has more electron density in between the nuclei.
This molecular orbital obtained by the addition of wave function (addition overlap of atomic
orbitals or constructive interference of electron waves) is called Bonding Molecular Orbital
[BMO].

Mathematically, Ψb = ΨA + ΨB

𝜳𝟐𝒃 = 𝜳𝟐𝑨 + 𝜳𝟐𝑩 + 2ΨA ΨB

Energy of Bonding Molecular orbital is less than the energy of the combining atomic orbitals.

2. If the two electron waves are out of phase, the amplitude of electron waves get subtracted
or cancelled (destructive interference of waves). The resulting wave has less electron density
in between the nuclei. This molecular orbital obtained by the subtraction of wave function
(subtraction overlap of atomic orbitals or destructive interference of electron waves) is
called Anti-Bonding Molecular Orbital [AMO].

Mathematically, Ψa = ΨA - ΨB

𝜳𝟐𝒂 = 𝜳𝟐𝑨 + 𝜳𝟐𝑩 ̶ 2ΨA ΨB

Energy of Ant-Bonding Molecular orbital is more than the energy of the combining atomic
orbitals.
Difference between Bonding and Ant-bonding Molecular Orbitals

Bonding Molecular Orbital Ant-bonding Molecular Orbital

1. It is formed when electron waves of [Link] is formed when electron waves of
combining atoms are in phase. combining atoms are out of phase.

2. The wave function of BMO is obtained by 2. The wave function of AMO is obtained
summing up the wave functions of the by subtracting the wave functions of the
combining atoms. (Ψb = ΨA + ΨB) combining atoms. (Ψa = ΨA ̶ ΨB)

3. The electron density concentrated between 3. The electron density between the nuclei
the nuclei of the combining atoms. of the combining atoms is negligible.

4. The energy of BMO is less than that of the 4. The energy of AMO is less than that of
combining atomic orbitals. the combining atomic orbitals.

[Link] in BMO lead to attraction [Link] in AMO lead to repulsion

between the combining atoms and stabilise between the combining atoms and
the molecule. destabilise the molecule.

Conditions for the combination atomic orbitals

1. The combining atomic orbitals should possess comparable energies.

For example, 1s orbital of an atom can overlap with 1s orbital but cannot overlap
with 2s orbital of another atom
2. The combining atomic orbitals must have proper orientation.
For example, 2px orbital always will of overlap with 2px orbital and cannot overlap
with 2py or 2pz orbital of another atom.

Formation of Molecular Orbitals.

• When atomic orbitals overlap along the internuclear axis (axial overlap), the molecular
orbitals formed are called sigma (𝝈) molecular orbitals.
• When the electron waves are in phase bonding sigma molecular orbital (𝝈) is formed.
• When the electron waves are out of phase anti-bonding sigma molecular orbital ( 𝝈∗ )
is formed.
• When atomic orbitals overlap sidewise, (parallel overlap), the molecular orbitals
formed are called pi (𝜋 ) molecular orbitals.
• When the electron waves are in phase bonding pi molecular orbital (𝜋) is formed.
• When the electron waves are out of phase anti-bonding pi molecular orbital ( 𝝅∗) is
formed.

Formation of Molecular orbitals from ‘s’ orbitals.

Overlapping of two ‘s’ orbitals takes place axially and sigma molecular orbitals are formed.
If the combining atomic orbitals are 1s and 1s, the bonding molecular orbital is represented
as 𝝈𝟏𝒔 and the anti-bonding molecular orbital as 𝝈∗ 𝟏𝒔.

Similarly, If the combining atomic orbitals are 2s and 2s, the bonding molecular orbital is
represented as 𝝈𝟐𝒔 and the anti-bonding molecular orbital as 𝝈∗ 𝟐𝒔.

subtraction

Addition

Formation of Molecular orbitals from ‘p’ orbitals.

Two p-orbitals can overlap axially or sidewise.

a) Axial Overlap. If Z-axis is the inter nuclear axis, the 2pz orbitals overlap axially to form two
𝜎 molecular orbitals. The bonding molecular orbital is represented as 𝝈𝟐𝒑𝒛 and antibonding
molecular orbital is represented 𝝈∗ 2𝒑𝒛 .

b) Sidewise Overlap. Sidewise overlap p-orbitals gives pi( 𝜋) molecular orbitals. Bonding
molecular orbital formed by the sidewise overlap of two 2px orbitals is 𝝅2px and the
antibonding molecular orbital is represented as 𝝅∗ 2𝒑𝒙 .

Similarly, side wise overlap of two 2py orbitals gives 𝝅2py and 𝝅∗ 2𝒑𝒚 molecular orbitals.

i) pz and pz combination
Differences between Sigma and Pi Molecular Orbitals

[Link] 𝝈- molecular orbitals 𝝅 − 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒂𝒓 𝒐𝒓𝒃𝒊𝒕𝒂𝒍𝒔

1. Formed by the axial overlap of atomic Formed by the sidewise overlap of atomic
orbitals. orbitals.
2. Overlapping is maximum. Overlapping is much less
3. The resulting covalent bond is strong. The resulting covalent bond is weak.
4. Free rotation about internuclear axis is Free rotation about internuclear axis is not
possible. possible.

Relative Order of Energies of Molecular Orbitals.

Following is the increasing order of energies of molecular orbitals for homonuclear diatomic
molecules such as Li2, Be2 B2 C2 and N2.

𝝈𝟏𝒔 < 𝝈∗ 𝟏𝒔 < 𝝈𝟐𝒔 < 𝝈∗ 𝟐𝒔 < 𝝅2px = 𝝅2py < 𝝈𝟐𝒑𝒛 < 𝝅∗ 2𝒑𝒙 = 𝝅∗ 2𝒑𝒚 < 𝝈∗ 2𝒑𝒛 .

In case of O2, F2 and Ne2, the increasing order of energies of molecular orbital is as follows.

𝝈𝟏𝒔 < 𝝈∗ 𝟏𝒔 < 𝝈𝟐𝒔 < 𝝈∗ 𝟐𝒔 < 𝝈𝟐𝒑𝒛 < 𝝅2px = 𝝅2py < 𝝅∗ 2𝒑𝒙 = 𝝅∗ 2𝒑𝒚 < 𝝈∗ 2𝒑𝒛 .

Filling up of molecular orbitals takes place according to Pauli’s principle, Hund’s rule and Aufbau
principle.
Bond Order.

It is defined as “one half of the difference between the number of electrons in bonding
molecular orbital and the number of electrons in antibonding molecular orbitals”.

Bond Order = ½ [number of electrons in BMOs – number of electrons in AMOs]

Bond order = ½ [Nb-Na] Where, Nb = number of electrons in Bonding Molecular Orbitals.

Na = number of electrons in Antibonding Molecular Orbitals.

• The bond order shows the number of covalent bonds present between a pair of atoms.
• The bond order describes the stability of the covalent bond. Greater the bond order
greater is the stability of the molecule or ion.
• Bond order may be +ve, ̶ ve , zero or fractional.
• A molecule or ion is stable only when the bond order is positive. When the bond order is
negative or zero, the molecule is unstable and does not exist.
• A molecule or ion having fractional bond order is paramagnetic.
• When the bond order is a positive whole number, the species may be paramagnetic or
diamagnetic.

Information from Bond Order.

1. Stability of molecule.

i) If Nb > Na, bond order is +ve and the molecule or ion is stable.

ii) if Nb < Na, bond order is ̶ ve and the molecule or ion is unstable and doesn’t exist.

iii) if Nb = Na, bond order is zero and the molecule or ion is unstable and doesn’t exist.

Greater the bond order greater is the stability of the molecule or ion.

2. Status of the bond.

Bond orders 1,2, and 3 correspond to single, double and triple bonds respectively.

3. Bond length . Higher the bond order, shorter is the bond length.
𝟏
Bond oder ∝
𝑩𝒐𝒏𝒅 𝒍𝒆𝒏𝒈𝒕𝒉

4. Bond Dissociation Energy .

Higher the value of bond order, greater is the bond dissociation energy

Bond order ∝ Bond dissociation energy

5. Magnetic Behaviour .

A molecule or ion having fractional bond order is paramagnetic. When the bond order
is a positive whole number, the species may be paramagnetic or diamagnetic.
M.O. Diagram and Electronic Configuration Of Some Homonuclear Diatomic Molecules.

1. Hydrogen Molecule (H2).

H – 1s1

H2 molecule contains two electrons.

Electronic Configuration of H2 - (𝛔𝟏𝐬)𝟐

Bond order = ½ [2-0] = 1.

Since bond order is equal to 1, hydrogen

atoms are joined by single bond.

Since bond order is +ve H2 molecule is stable.

H2 molecule contains only paired electrons. Hence it is diamagnetic.

2. Hydrogen Molecular Cation (H2+).

H – 1s1, H+ – 1s0

H2+ ion contains one electron .

Electronic Configuration of H2+ - (𝝈𝟏𝒔)𝟏

Bond order = ½ [1-0] = 0.5

Since bond order is +ve H2+ is stable, but less stable than H2

H2+ contains an unpaired electron. Hence it is paramagnetic.

3. Hydrogen Molecular anion (H2̶ ) .

H – 1s1, H ̶ = 1s2

H2 ̶ ion contains three electrons .

Electronic Configuration of H2 ̶ - (𝝈𝟏𝒔)𝟐 (𝝈∗ 𝟏𝒔)𝟏

Bond order = ½ [2-1] = 0.5

Since bond order is +ve H2 ̶ is stable, but less stable than H2,

But less stable than H2+ ion because, presence of electron in antibonding orbital
destabilises the ion

H2 ̶ contains an unpaired electron. Hence it is paramagnetic.

[Link] Molecule (He2). (hypothetical)

He- 1s2, He2 has four electrons. Electronic configuration of He2 - (𝝈𝟏𝒔)𝟐 ( 𝝈∗ 𝟏𝒔)𝟐
Bond order = ½ [2-2] = 0. Hence He2 cannot exist.
[Link] Molecule ion (He2+).
He- 1s2, He+- 1s1.
He2+ has three electrons. Electronic configuration of He2+ -( 𝝈𝟏𝒔)𝟐 (𝝈∗ 𝟏𝒔)𝟏
Bond order = ½ [2-1] = 0.5
Due to the presence of unpaired electron, it is paramagnetic.

5. Lithium Molecule (Li2).

Li – 1s2,2s1.
Li2 has six electrons.
Electronic configuration of Li2+ = KK (𝝈𝟐𝒔)𝟐
Bond order = ½ [2-0] = 1.

Li atoms are joined by single bond.

Li2 molecule contains only paired electrons.

Hence it is diamagnetic

6. Beryllium Molecule (Be2) (hypothetical)

Be – 1s2,2s2. Be2 has six electrons.
Electronic configuration of Be2 = KK (𝝈𝟐𝒔)𝟐 , (𝝈∗ 𝟐𝒔)𝟐
Bond order = ½ [2-2] = 0. Hence Be2 can not exist.

7. Boron molecule (B2)

B – 1s2, 2s2, 2px1.
B2 has ten electrons.
Electronic Configuration of

B2 = KK (𝝈𝟐s)2, (𝛔*2s)2, (𝝅2px)1 = (𝝅2py)1

Bond order = ½ [4-2] = 1.

Boron atoms are joined by single bond.

B2 molecule contains two unpaired electrons.

Hence it is paramagnetic.

8. Carbon Molecule (C2)

C– 1s2, 2s2, 2px1, 2py1.
C2 has twelve electrons.
Electronic Configuration of -

C2 = KK (𝝈𝟐s)2, (𝛔*2s)2, (𝝅2px)2 = (𝝅2py)2

Bond order = ½ [6-2] = 2.

Carbon atoms are joined by double bond
C2 molecule contains only paired electrons.

Hence it is diamagnetic.
9. Nitrogen Molecule. (N2).

N– 1s2, 2s2, 2px1, 2py1 2pz1

N2 has fourteen electrons.
Electronic Configuration of -

N2 = KK (𝝈𝟐s)2, (𝛔*2s)2, (𝝅2px)2 = (𝝅2py)2, (𝝈𝟐pz)2

Bond order = ½ [8-2] = 3.

Nitrogen atoms are joined by triple bond
N2 molecule contains only paired electrons.

Hence it is diamagnetic.

10. Oxygen Molecule (O2)

O– 1s2, 2s2, 2px2, 2py1 2pz1 . O2 has sixteen electrons.

[Link]. of O2 = KK (𝝈𝟐s)2, (𝛔*2s)2, (𝝈𝟐pz)2,(𝝅2px)2 = (𝝅2py)2, (𝝅∗2px)1 = (𝝅∗2py)1

Bond order = ½ [8-4] = 2.

Oxygen atoms are joined by double bond.

O2 molecule contains two unpaired electrons.

Hence it is paramagnetic.

Thus, M.O. theory easily explains the

Paramagnetic character of O2molecule.

Question. Arrange the following species in the increasing order of their stability.

O2, O2̶ , O2+ and O22-

1. O2 molecule.
O – 1s2, 2s2, 2px2, 2px1 2pz1 . O2 has sixteen electrons.
[Link]. of O2 = KK (𝜎2s)2, (σ*2s)2, (𝜎2pz)2,(𝜋2px)2 = (𝜋2py)2, (𝜋 ∗ 2px)1 = (𝜋 ∗ 2py)1

Bond order = ½ [8-4] = 2.

O2 molecule contains two unpaired electrons. Hence it is paramagnetic.
2. super oxide ion (O2̶ ). O2̶ has fifteen electrons.
[Link]. of O2 = KK (𝜎2s)2, (σ*2s)2, (𝜎2pz)2,(𝜋2px)2 = (𝜋2py)2, (𝜋 ∗ 2px)2 = (𝜋 ∗ 2py)1

Bond order = ½ [8--5] = 1.5

̶
O2 ion contains one unpaired electron. Hence it is paramagnetic.

3. Oxygen molecule ion (O2+). O2+ has fifteen electrons.

[Link]. of O2 = KK (𝜎2s)2, (σ*2s)2, (𝜎2pz)2,(𝜋2px)2 = (𝜋2py)2, (𝜋 ∗ 2px)1 = (𝜋 ∗ 2py)0

Bond order = ½ [8--3] = 2.5

O2 + ion contains one unpaired electron. Hence it is paramagnetic.

4. Peroxide ion ( O22̶ ) O22- has eighteen electrons.

[Link]. of O2 = KK (𝜎2s)2, (σ*2s)2, (𝜎2pz)2,(𝜋2px)2 = (𝜋2py)2, (𝜋 ∗ 2px)2 = (𝜋 ∗ 2py)2

Bond order = ½ [8--4] = 1

O22- ion contains only paired electrons. Hence it is diamagnetic.

Higher the bond order greater is the stability. Thus, the stability of O22-< O2- < O2 < O2+.

11. Fluorine Molecule (F2)

F – 1s2, 2s2, 2px2, 2px2 2pz1 . F2 has eighteen electrons.

[Link]. of F2 = KK (𝝈𝟐s)2, (𝛔*2s)2, (𝝈𝟐pz)2,(𝝅2px)2 = (𝝅2py)2, (𝝅∗2px)2 = (𝝅∗2py)2

Bond order = ½ [8-6] = 1.

Fluorine atoms are joined by single bond.

F2 molecule contains only paired electrons.

Hence it is diamagnetic.

Energy

F F
F2
11. Neon Molecule (Ne2) (hypothetical)

Ne– 1s2, 2s2, 2px2, 2px2,2pz2 . Ne2 has twenty electrons.

[Link]. of Ne2 = KK (𝝈𝟐s)2, (𝛔*2s)2, (𝝈𝟐pz)2,(𝝅2px)2 = (𝝅2py)2, (𝝅∗2px)2 = (𝝅∗2py)2,
(𝝈∗ 2𝒑𝒛 )2

Bond order = ½ [8-8] = 0. Hence Ne2 cannot exist.