Chapter 01

Atomic and Molecular Structure

Atom:
“It is the smallest particle of element which cannot be further sub-divided and which can take
part in all chemical changes. It may or may not be capable free existence”.
Ex. H – atom, O – atom, N – atom etc.

Molecule:
“It is the smallest particle of an element or a compound that can exist in a free state and retain
all its properties”.
Ex. Cl2, H2O, H2 etc.

Fundamental Particles of an Atom (Sub – atomic particles)

Atom
(Neutral)

Nucleus Extra nuclear part

(Positively charged) (Negatively charged)

Planetary electrons
Protons Neutrons (Negatively charged)
(Positively charged) (Neutral)

Structure of Atom
 Characteristic Electron Proton Neutron
Discovered by J. J. Thomson Goldstein Chadwick
In 1896 In 1911 In 1932
Symbol E p N
Location Outside nucleus Inside nucleus Inside nucleus
Mass in amu 0.000555 1.007825 1.008665
charge -1 +1 0

• Concept of Shells (Main Energy Level), Sub- shells (Sub – sub energy level) and
Orbitals:

➢ Shells (Main Energy Levels)

Bohr’s stationary orbits with definite amount of energy are called energy levels or energy states or
Shells.

Shells Orbit (n) Max. no. of e’s (2n2)

K 1 2 x 12 = 2

L 2 2 x 22 = 8

M 3 2 x 32 = 18

N 4 2 x 42 = 32

➢ Sub-Shells (Sub-energy levels)

The close grouping of a number of energy levels in the main energy level are called Sub-energy levels.
They are denoted by s, p, d, and f
 Sub – Energy Levels

S P D F
Sharp Principal Diffused Fundament
Spherical Dumbbell Spherical & Spherical
Shape Shape dumbbell double dumbbell
(l=0) (l=1) (l=2) (l=3)

1s Orbital 3p Orbitals 5d Orbitals 7f Orbitals

1s px py pz dxy dyz dzx dx2ydz2

2(2l+1)

2 electrons 6 electrons 10 electrons 14 electrons

Main-Energy Levels

Shells K L M N

Sub- s s, p s, p, d s, p, d, f
Shells Sub-level Sub-level Sub-level Sub-level

Orbital 1s 2s, 2p 3s, 3p, 3d 4s, 4p, 4d, 4f

OrbitalOrbitalOrbitalOrbital

No. of 2 2+6=8 2+6+10=18 2+6+10+14=32

e’s electrons electrons electrons electrons
• Graphical Representation of Sub-Shells

3d
4s
n=4(N)
Energy 3p
Increasing 3s
n=3(M)
2p
2s
n=2(L)
1s
n=1(K)
Sub-energy levels

• Difference between Orbit and Orbital

Sr. ORBITS ORBITALS

No.

1. Orbit is a fixed circular path described by a Orbital is a 3 Dimensional region in space

moving e- around a nucleus. around the nucleus, where there is maximum
probability of finding an electron.

Maximum capacity of any orbital is 2

2. Maximum capacity of any orbit is 2n2 electrons.
electrons, where n is the number of orbit.
Orbitals have different geometrical shapes
3. Orbits are circular paths or elliptical in shape. i.e. Spherical, dumbbell shaped.

The position and velocity of a moving e-in an The position and velocity of moving
4. orbit can be calculated with great accuracy. electronin an orbital can be determined in
accordance with the uncertainty principle.

The distance of the orbit from the nucleus for It is not possible to know the exact distance
a given e-is fixed. of e-from nucleus.
5.
The orbits are designated by the letters K, L, The orbitals are designated by letters s, p, d,
M, N etc. f etc.
6.

• What are Quantum Numbers? Explain them in detail.

➢ Quantum Numbers: - “It may be defined as a set of four numbers (n, l, m, s) with the help of which
we can get complete information about all the electrons in an atom location, energy the type of orbital
occupied shape and orientation of that orbital”.
There are four quantum numbers:
1. Principal quantum number (n)
2. Azimuthal quantum number (l)
3. Magnetic quantum number (m)
4. Spin quantum number (s)

1. Principal quantum number (n)

a) This number represents the main shell to which the electron belongs.
b) It determines the average distance of an element from the nucleus and its energy level.
c) It provides information about the energy of the principal shell.
d) It represents the size of the electron orbital higher the value of n, larger is the size of orbital and the
energy of the orbital increases.
e) ‘n’ can have positive integral values 1, 2, 3, 4 corresponding to K, L, M, N etc.
f) Maximum number of electrons in a shell is given by 2n2.

Main energy level (n) 1 2 3 4

Letter designation K L M N
Maximum no. of electrons (2n2) 2 8 18 32

2. Azimuthal quantum number (l)

a) It is also called secondary, subsidiary quantum number.
b) It represents the sub-shells to which the electron belongs.
When
l=0, ‘s’ sub-shell
l=1, ‘p’ sub-shell
l=2, ‘d’ sub-shell
l=3, ‘f’ sub-shell
c) It indicates the shape of the orbital i.e. whether the orbital is spherical, dumbbell shaped or some
more complicated shape.
d) The value of ‘l’ depends upon the value of ‘n’ hence l can have the values from 0 to (n-1)
l= 0, 1, 2, 3 - - - - - (n-1)
When
n=1, l=0
n=2, l=0 &1
n=3, l=0, 1 & 2
n=4, l=0, 1, 2 & 3
e) This quantum number determines the angular momentum of an electron in a particular orbital.
ℎ
𝐿= √𝑙 ( 𝑙 + 1 )
2𝜋
Where
L = Angular momentum
 h = Plank’s constant

3. Magnetic quantum number (m)

a) It determines the orientation of the orbital relative to the magnetic field in which it is placed.
b) The values of ‘m’ depends on the value of ‘l’. For each value of l, the ‘m’ may have (2l + 1) values.
These values range from –l through zero to + l.
When l= 0, m = 0
l = 1, m = - 1, 0, + 1
l = 2, m = - 2, - 1, 0, + 1, + 2
l = 3, m = - 3, - 2, - 1, 0, + 1, + 2, + 3

4. Spin quantum number (s)

a) It indicates the direction in which the electron is spinning about its own axis.
b) The electron can spin clockwise () or anticlockwise (), in two opposite directions.
c) Spin quantum numbers can have two possible values +½ and - ½ depending on the direction of spin.
d) Only 2 electrons can be accommodated in the orbital with opposite spin ()

Permitted Values of Total Quantum Numbers.

Principal Q.N Azimuthal Q.N Magnetic Q.N Spin Q.N Total no. of
(n) (l) (m) (s) e’s in shell
Value Abbreviation 0 to (n - 1) 2l+1 2n2
of N

1 K l = 0(s) m=0 ±½ 2
 2 L l = 0(s) m=0 ±½ 8
l = 1(p) m = -1, 0, +1 ±½

3 M l = 0(s) m=0 ±½
l = 1(p) m = - 1, 0, + 1 ±½ 18
l = 2(d) m = -2, -1,0, +1, +2 ±½

4 N l = 0(s) m=0 ±½
l = 1(p) m = - 1, 0, + 1 ±½
l = 2(d) m = -2, -1,0, +1, +2 ±½ 32
m = - 3,- 2, -1, 0, ±½
l = 3(f) +1, +2, +3

• Explain the shapes of different types of atomic orbitals.

1. S - Orbital
a) The lowest energy orbital of an atom is known as s – orbital.
b) For s – orbital, l= 0 and for l= 0, m= 0
Therefore s – orbital have only one orientation.
c) S – Orbitals are spherically symmetrical about the nucleus.
d) r
e) In between 1s and 2s, there is a region where probability of finding the electron is zero. It is called
as ‘node’.
 Increasing size of S – orbitals

2. P – Orbitals
a. For p – orbitals, l= 1 and for l= 1, m = +1, 0, -1
b. Thus p – orbitals have three orientations.
c. P – orbital is ‘dumbbell’ shaped consisting of two lobes.
d. Three p – orbitals px, py and pz are perpendicular to each other and oriented along x, y and z axes
respectively in space.
e. They ae equivalent in energy in absence of magnetic field.
f. Orbitals, which differ in orientation but having equal energy, are called ‘degenerate orbitals’.
g. The two lobes are separated by a plane having zero electron density such a plane is called ‘nodal
plane’.
3. D - Orbitals
a. For d – orbitals, l= 2 and for l= 2, m = +2, +1, 0, -1, -2
b. Thus d – orbitals have five orientations.
c. They are designated as dxy, dyz, dzx,dx2- y2, dz2.
d. They are equivalent in energy in absence of magnetic field, so they are also degenerate orbitals.
e. Out of five orbitals, the first three have double dumbbell shapein xy, yz and xz plane respectively.
The dx2- y2is also double dumbbell shaped lying along the x and y-axes.
The dz2is dumbbell shaped with a doughnut shaped ring of high electron density around the
nucleus in xy plane.
• What does Electronic Configuration of an element means? Explain the rules to be
followed for filling the electrons.

Electronic Configuration: The distribution of electrons in various orbitals of an atom is known as

electronic configuration. It is written as nlx, where n = shell number, l= sub shell and x = no. of e’s.
E.g.: 3p2where n = 3, l = 1, x = 2

Electronic configuration is mainly explained by following rules:

1. Aufbau Principle
2. Pauli’s Exclusion Principle
3. Hund’s rule of maximum multiplicity.

1. Aufbau Principle

It states, “The electrons always enter the various orbitals in order of their increasing energies”.
According to Aufbau Principle, in the ground state of an atom, the orbital with lower energy is
filled first before the filling of the orbital with higher energies.

The order of energy of different orbitals in an atom is given as:

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p < 7s < 5f < 6d < 7p < 8s
< 6f < 7d and so on.

2. Pauli’s Exclusion Principle

It states, “No two electrons in a single atom can have the same set of four quantum numbers”.
Therefore, any orbital can have a maximum of only two electrons in opposite spin.
E.g.: Consider He atom having atomic no. 2 and electronic configuration as1s2.
 Electron Quantum Number
Number n l m s
1st electron 1 0 0 +½
2nd electron 1 0 0 -½

It show that two electrons existing in the same orbital can have 3 quantum numbers same but the
fourth will be different.

3. Hund’s Rule of Maximum Multiplicity

It states, “No pairing takes place in degenerate orbitals until and unless each orbital is singly
occupied”.
When several orbitals of equal energy (degenerate orbitals) are available, the electrons first fill all
the orbitals singly before pairing in any of these orbitals.
E.g.the configuration of four electrons occupying p – orbitals is

• Write the electronic configuration of 30 elements of the periodic table.

H (1) -1s1
He (2) - 1s2
Li (3) -1s2 2s1
Be (4) -1s2 2s2
B (5) -1s2 2s22p1
C (6) -1s2 2s22p2
N (7) -1s2 2s22p3
O(8) -1s2 2s22p4
F (9) -1s2 2s22p5
N (10) -1s2 2s22p6
Na (11) - [Ne] 3s1
Mg (12) - [Ne] 3s2
Al (13) - [Ne] 3s23p1
Si (14) - [Ne] 3s23p2
P (15) - [Ne] 3s23p3
S (16) - [Ne] 3s23p4
Cl (17) - [Ne] 3s23p5
Ar (18) - [Ne] 3s23p6
K (19) - [Ar] 4s1
1s2 2s22p63s23p64s1
Ca [20] - 1s2 2s22p63s23p64s2
Sc [21] - 1s2 2s22p63s23p63d14s2
Ti [22] - 1s2 2s22p63s23p63d24s2
V [23] - 1s2 2s22p63s23p63d34s2
 Cr [24] - 1s2 2s22p63s23p63d54s1
Mn [25] - 1s2 2s22p63s23p63d54s2
Fe [26] - 1s2 2s22p63s23p63d64s2
Co [27] - 1s2 2s22p63s23p63d74s2
Ni [28] - 1s2 2s22p63s23p63d84s2
Cu [29] - 1s2 2s22p63s23p63d104s1
Zn [30] - 1s2 2s22p63s23p63d104s2

Anomalies in electronic configuration

1. Cr (24)
Expected electronic configuration - 1s22s22p63s23p64s23d4
Observed electronic configuration - 1s22s22p63s23p64s13d5

The 3d orbital is not half filled. Hence, it is less stable. One 4s orbital e shifts to empty 3d orbital to
make 4s and 4d orbitals half filled. Thus, Cr acquires stability as its electronic configuration becomes
half-filled 4s and 3d.

2. Cu (29)
Expected electronic configuration - 1s22s22p63s24s23d9
Observed electronic configuration - 1s22s22p63s24s13d1

The 3d orbital is neither half-filled nor completely filled. Hence, it is less stable. One 4s electron shifts
to one half-filled 3d orbital to make 4s half-filled and 3d completely filled. Thus Cu acquires stability
as its electronic configuration become 4s13d10. In this configuration, 3d orbital is completely filled and
4s orbital is half-filled which gives extra stability to Cu.

Molecular Orbital Theory (MOT)

It is a quantum mechanical approach in which the atomic orbitals combine to form new orbitals called
molecular orbitals.
MOT was developed to explain:
➢ The formation of chemical bond.
➢ Relative bond strength.
➢ Paramagnetic or diamagnetic nature of molecules.

These properties were not explained by VBT (Valence bond theory). VBT explained stability of
covalent bond and molecular geometrics. Therefore, this was the fundamental deficiency in VBT.

• What is molecular orbital theory? Give its postulates.

➢ The following are the main postulates of molecular orbital theory:

1. In the formation of a molecule, atoms come close to each other, interact and form bonds between them.
2. The number of MO formed is equal to the number of overlapping atomic orbitals.
3. The MO are formed by the mixing of atomic Orbitals of same energy levels and symmetry.
 4. The atomic orbitals lose their identity after formation of molecular orbitals.
5. All the electrons present in the MO are considered to be moving under the influence of all the nuclei of
the molecules.
6. Atoms have atomic orbitals with one nucleus whereas molecules have molecular orbitals with n
nucleus. Therefore, atoms are monocentric while molecules are polycentric.
7. Molecular orbitals can be divided in 3 categories:
a. Bonding molecular orbitals (BMO)
b. Anti-bonding molecular orbitals (ABMO)
c. Non-bonding molecular orbitals (NBMO)
8. BMO have lower energy than the corresponding anti-bonding molecular orbitals.
9. Each MO is described by a quantum mechanical wave function, which is associated with a set of
quantum number.
10. Electrons fill up in the MOs in the same way as in atomic orbitals by following the rules like Aufbau
principal, Pauli’s exclusion principle and Hund’s rule of maximum multiplicity.
11. The molecular orbitals for a molecule can be constructed by using LCAO (Linear combination of
Atomic Orbitals) method.
12. The shape of MO formed depends on the type of combining atomic orbitals.
13. Inner Molecular orbital, which do not take part in bond formation, are called non-bonding MO.

• Explain combination of atomic orbitals by LCAO method.

1. According to quantum mechanics, the atomic orbitals can be expressed as wave functions (ᴪ) which
represent the amplitude of electron waves.
2. According to LCAO method, the molecular orbitals are formed by the linear combination (addition or
subtraction) of atomic orbitals of the molecule.
3. By combining the atomic orbitals A & B, we get two molecular orbitals:
ᴪb = ᴪA + ᴪB
ᴪa = ᴪA - ᴪB
Where ᴪA = atomic orbital of atom A
ᴪB = atomic orbital of atom B
ᴪb = wave functions of bonding molecular orbital
ᴪa = wave functions of anti-bonding molecular orbital
4. The MO with highest energy gives to a repulsive state and is called anti-bonding MO (ᴪa).
5. The MO with lower energy gives rise to an attractive state and is called as bonding MO (ᴪb)
• Explain the Bonding molecular orbitals and Anti-bonding molecular orbitals with
example.

A wave has crest and trough, which is a property of wave function ᴪ having positive and negative
signs.

Crest

Trough

Atomic orbitals combine and form the same number of molecular orbitals by either addition or
subtraction of atomic orbitals.

a) Bonding Molecular Orbitals (BMO)

When the atomic orbitals with the same sign combine, their wave functions are in the same phase. This
kind of combination gives rise to BMO.
When combination of AO’s takes place by addition, both the electron waves are on the positive side
i.e. the same side or in same phase.

Combination of two 1S AO’s by addition

 Formation of BMOs by addition of two AOs

In this molecular orbital, the region between the two uncle’s is the place where there is over lap of the
individual orbitals and hence there is greater probability of electrons density in the region.

b) Anti-bonding Molecular Orbitals (ABMO)

When the atomic orbitals with the opposite sign combine, their wave functions are out of phase. This
kind of combination gives rise to anti-bonding molecular orbitals. They are designated as asterisk (*).
When combination of AO’s takes place by subtraction, their wave functions are in the opposite
directions having wave functions of different signs or out of phase.

Combination of two 1S AO’s by subtraction.

 Formation of ABMOs by subtraction of two AOs.

In anti-bonding orbitals, the electrons are in those regions in space where they are not under the
attraction of both the nuclei.
 • What are the conditions for the combination of atomic orbitals?

Conditions for the formation of molecular Orbitals

1. The energies of combining atomic orbitals should be same or nearly same.

E.g.1s orbital can combine with another 1s orbital but not with 2s orbital, as 2s orbital is having higher
energy than 1s orbital.

2. The combining atomic orbitals should possess same symmetry about the molecular axis.
E.g.2pz orbital can combine with 2pz and not with 2px or 2py orbitals because of their different
symmetries.

3. The combining atomic orbitals must overlap to the maximum extent. Greater the extent of overlap, the
greater will be the electron density between the nuclei of molecular orbital.

• What are sigma (σ) and pi (π) molecular orbitals?

OR
Sketch and describe the molecular orbital resulting from the combinations of different
atomic orbitals.

1. Molecular orbitals of a diatomic molecule are designated as σ(sigma) and π(pi).

2. When two AOs overlap along the inter nuclear axis (head on collision), then the resulting molecular
orbital is called σ (sigma) MO.
3. When two AOs overlap laterally (sideways), then the resulting MO is called π(pi) MO.

Combination of Different AOs

Head on Overlapping Sideways Overlapping

(σ) MO (π) MO

‘S-S’ ‘S-pz’‘Pz – Pz’‘Py – Py’ ‘Px – Px’

combination combination combinationcombination
 σ1s / σ2s σ*1s / σ*2s σspz σ*spz σPz σ*Pz πPy = πPx π*Py = π*Px

a) S – S Combination of orbitals (1s with 1s / 2s with 2s)

1. The overlap is along inter nuclear axis.

2. Constructive overlapping forms σ1s / σ2s.
3. Destructive overlapping forms σ*1s / σ*2s.
4. The two BMOs formed are σ (1s) or σ (2s) and anti-bonding MOs are σ*(1s) or σ*(2s).

Addition

S S

Bonding orbitals (σs)

AO’s Node

Subtraction

Anti-bonding orbitals (σ*s)

b) S – P Combination of orbitals (S- orbital with Pz orbital)

1) It is a coaxial overlap of S & pz orbitals.

2) S – Orbital can combine with p – orbital when the lobes of p – orbital are pointing along the axis
joining the nuclei.
3) When same sign lobes overlap, BMO is formed (σsp) with an increased e-density between the nuclei.
4) When opposite sign lobes overlap, ABMO is formed (σ*sp) with reduced e- density in between the
nuclei.
c) Axial p – p combination of orbitals (Pz with Pz)

1) It is axial overlap of pz-pz orbitals.

2) Lobes of combining orbitals point along the axis joining the nuclei.
d) Side to side p-p combination (Py-Py / Px-Px)

1) It is side-to-side overlap of Py-Py or Px-Px.

2) Lobes of combining orbitals are perpendicular to the axis joining the nucleus.
• Explain the formation of molecular orbitals in diatomic molecules.
OR
Give the rules for writing MO electronic configuration.

1) To understand the physical and chemical properties of molecules, we should know how electrons are
distributed in molecular orbitals.
2) The procedure for determining the electronic configuration of a molecule is same as the electronic
configuration of atoms.
3) For writing the electronic configuration of a molecule, we should first arrange the MOs in the order of
increasing energy.
4) The relative order of energy of MOs is:
(σ1s <σ*1s <σ2s <σ*2s <σ2pz <π2px = π2py <π*2px = π*2py <σ*2pz)
5) The distribution of electrons in the molecular orbitals is on the basis of:

a) Aufbau principle: Molecular orbitals are filled in order of increasing energy.

b) Pauli’s exclusion principle: Two electrons in the same orbital cannot have set of all the four
quantum numbers identical. It means maximum two electrons can occupy a molecular orbital with
opposite spin ( ).

c) Hund’s rule of maximum multiplicity: Pairing of electrons in the degenerate molecular orbitals
does not occur until each of them has one e- each.

6) Σ molecular orbital is more stable as compared to π molecular orbital.

7) The number of e-s in the MO is equal to the sum of all the e-s on the bonding atoms.
8) The e-s associated with bonding MO are known as bonding e-s and e-s in the anti-bonding orbital are
known as anti-bonding e-s.
• What are the atomic orbitals, which can combine for the formation of a diatomic
molecule?

Atomic Orbitals Molecular Orbitals

1sA + 1sB σ1s

1sA – 1sB σ*1s
2sA + 2sB σ2s
2sA – 2sB σ*2s
2pzA + 2pzB σ2pz
2pzA – 2pzB σ*2pz
2pyA + 2pyB π2py
2pxA + 2pxB π2px
2pyA - 2pyB π*2py
2pxA - 2pxB π*2px

• Give diagrammatic representation of the energy levels of the molecular orbitals in

diatomic molecules.
• What are the properties of a molecule that can be explained on the basis of molecular
orbital energy diagram?

The electronic configuration in the molecular orbital can explain certain facts and the properties
observed for a molecule. The following properties can be explained:-

a) Stability of the molecule:

If Nb is the number of e-s present in BMO and Na is the number of e-s present in ABMO, then
1) If Nb is greater than Na i.e. Nb>Na – stable molecule.
2) If Nb is less than Na i.e. Na<Na – Unstable molecule.

b) Bond order (BO):

 The bond order is defined as half the difference between the number of e-s present in the bonding and
anti-bonding molecular orbitals. i.e.

1 𝑁𝑏−𝑁𝑎
Bonding order (𝐵𝑂) = (𝑁𝑏 − 𝑁𝑎) =
2 2

1) A positive BO means stable molecule.

2) A negative BO or zero BO means unstable molecule.

c) Number and nature of bonds :

1) The BO values of +1, +2, +3 indicates that the molecule is formed by joining of two atoms by a single,
double or triple bond respectively.
2) Greater the value of BO, greater is the stability of the molecule.
3) Bond length is inversely proportional to BO.
4) Higher the bond order, higher is the dissociation energy.

d) Magnetic nature :

1) If the MO contains one or more unpaired electrons, the molecule is paramagnetic in nature. I.e. singly
occupied () – paramagnetic.
2) If the MO does not have any unpaired electron i.e. if all electrons are paired, then the molecule is
diamagnetic in nature. I.e. doubly occupied ( ) – diamagnetic.

• Explain in detail the MO diagram for the following Homo nuclear Diatomic molecules:
(1) Be2 (2) O2
OR
Explain on the basis of MOT, Why Be2 molecule does not exist?

1. Be molecule may be formed by the overlap of two Be atoms.

2. Each Be atoms have electronic configuration as Be(4) = 1s22s2.
3. Therefore, there are total of eight electrons from two Be atoms to be filled in the molecular orbitals.
4. The eight e-s are filled in four molecular orbitals i.e. σ1s, σ*1s, σ2s & σ*2s according to Aufbau
principle and Pauli’s exclusion principle.
5. MO electronic configuration of Be2 molecule = σ1s2σ*1s2σ2s2σ*2s2
Or Be2 molecule = kk σ2s2 σ*2s2
6. The inner shell of filled σ1s & σ*1s MOs do not take part in bond formation, i.e. they are non-bonding.
So, sometimes it is written as KK that means K-shell is completely filled.
7. The remaining 2s orbitals of both Be atoms having 4 e-s will be filled in σ2s &σ*2s molecular orbitals.
𝑁𝑏−𝑁𝑎
8. The bond order (BO) of Be2 molecule =
2
2−2
= =0
2
9. Since the BO is zero, Be2 is an imaginary, unstable non-existent molecule.
10. It indicates that formation of diatomic (Be2) is not possible.
• Explain the structure of O2 molecule by MO theory. Show that O2 is paramagnetic
according to MO theory.

1. O2 molecule is formed by the overlap of two oxygen atoms each having electronic configuration as
0(8) = 1s22s22p4
2. Therefore, O2molecule has total 16 electrons to be filled in Mos.
3. As 1s orbitals are considered to be non-bonding, the 4 electrons of σ1s2& σ*1s2 are ignored.
4. The remaining 12 electrons are filled in MO.
5. The MO electronic configuration of O2 molecule is
O2 = KK σ2s2σ*2s2σ2px2π2px2 = π2py2π*2px1π*2py1
 𝑁𝑏−𝑁𝑎 8−4
6) Bond order (BO) = = =2
2 2
7) Bond order of two suggests that O2 molecule has double bond (0 - 0), one σ(sigma) and one π (Pi)
bond between two O atoms.
8) The bond order of 2 also suggests that the O2 molecule is quite stable.
9) Presence of two unpaired electrons in its π*2px and π*2py indicates that O2 molecule is paramagnetic
in nature.

• Explain in detail the molecular orbital diagram of the hetero nuclear diatomic molecule
(CO).

➢ Molecular orbital Diagram of CO molecule

1. CO molecule is formed by the overlap of carbon and oxygen atom.

2. The electronic configuration of C & O are as follows:
C (6) = 1s22s22p2
O (8) = 1s22s22p4
3. There are total 14 electrons to be filled in MOs’
4. CO is hetero nuclear molecule in which oxygen is more electronegative than carbon. Therefor
atomic orbitals of oxygen are at lower energy level than the atomic orbitals of carbon. As the
bonding MOs are closer to oxygen AOs, they contribute more to the MOs’ this unequal
contribution of carbon and oxygen atoms to the MOs make CO molecule polar in nature.
5. Out of 14 electrons, four electrons are filled in non-bonding orbital i.e. σ1s & σ*1s as they are
inner shells.
6. The remaining 10 electrons will be filled in MOs
7. The MO electronic configuration of CO is
CO = KK σ2s2 σ*2s2π*2px2 = π*2py2σ2pz2
Where KK the two non-bonding 1s orbital of C & O atoms.

𝑁𝑏−𝑁𝑎 8−2
8. Bond order = = =3
2 2
 9. The BO of three indicates that there is triple bond between C & O (C ≡ O), one sigma (σ) and two
pi (π) bonds.
10. As BO is three, which is very high, CO is a very stable molecule.
11. As all the electrons are paired, CO is diamagnetic in nature.

Note:Based on 14 electron rule, if the total number of e-s in a molecule is less than or equal to 14,
then the σ2pz MO is higher in energy as compared to π2px and π2py.
Therefore, In MO diagram of CO, σ2pz is above than π2px = π2py.

• Explain in detail the molecular orbital diagram for the hetero nuclear diatomic molecule
(NO).

➢ Molecular orbital diagram of NO molecule

1. NO molecule is formed by the overlap of Nitrogen and oxygen atoms.

2. The electronic configuration of N & O are as follows:
N (7) = 1s22s22p3
O (8) = 1s22s22p4
3. There are total 15 electrons to be filled in MOs’
4. NO is hetero nuclear molecule in which oxygen is more electronegative than N. Therefore, AOs of
oxygen are at lower energy level than the AOs of nitrogen.
5. As the bonding MOs are closer to oxygen AOs, they contribute more to the MOs’ this unequal
contribution of N & O atoms to the MOs make NO molecule polar in nature.
6. Out of 15 electrons, four electrons form non-bonding orbital.
7. Remaining 11 electrons to be filled in MOs
8. The MO electronic configuration of NO is
NO = KK σ2s2 σ*2s2 σ2pz2π2px2 = π2pz2 π*2px1or π*2py1
Where KK represents the two non-bonding 1s orbital of N & O atoms.
 𝑁𝑏−𝑁𝑎 8−3
9. Bond order (BO) = = = 2.5
2 2
10. BO of 2.5 indicates that bond between N & O is between a double and triple bond.
11. Between N & O (N O), one is sigma (σ) and one & half is Pi (π) bonds.
12. NO molecule is stable due to the presence of one unpaired e- in antibonding MO that creates
charge over both the atoms.
13. NO molecule is paramagnetic in nature due to the presence of one unpaired e- in antibonding MO.
❖ NO+ is more stable than NO
Because BO of NO+ = 3. This leads to strengthening & shortening of bond length as a single
bond is longer, double bond is shorter & triple bond is still shorter in length.

• Differentiate between bonding and antibonding molecular orbitals.

 Bonding MO Anti-bonding MO

1) Formed by addition overlap of atomic 1) Formed by subtraction overlap of atomic

orbitals. orbitals.

2) Wave function of a bonding MO is given by 2) Wave function of an anti-bonding MO is

ᴪb = ᴪA + ᴪB given by ᴪa = ᴪA - ᴪB

3) A BMO forms when the lobes of atomic 3) A BMO forms when the lobes of atomic
orbitals have same sign. orbitals have different sign.

4) Possesses lower energy and hence is more 4) Possesses higher energy and hence is less
stable than the overlapping atomic orbitals. stable than the overlapping atomic orbitals.

5) The e- density between the two nuclei is 5) The e- density between the two nuclei is nil
maximum and results in less inter nuclear and results in more inter nuclear repulsion.
repulsion.
6) Imparts instability to the molecule.
6) Imparts stability to the molecule.

• Differentiate between sigma (σ) and pi (π) MOs.

Sigma (σ) MO Pi (π) MO

1) Formed by head on collision of AOs. 1) Formed by lateral overlap of AOs.

2) The lobes of the AOs are along the 2) The lobes of the AOs are perpendicular to
internuclear axis. the internuclear axis.

3) The electron density along the 3) The electron density along the
internuclear axis is not zero (ᴪ2 ≠ 0). internuclear axis is zero (ᴪ2 = 0).

4) Σ BMOs are gerade (even) and σ*ABMOs 4) π BMOs are ungerade (uneven) and
are ungerade (uneven). π*ABMOs are gerade (even).

5) Strength of overlapping is greater, therefore 5) Strength of overlapping is less, therefore

forms stronger bonds. forms comparatively weaker bonds.