CHEMISTRY R23

UNIT- 1
STRUCTURE AND BONDING MODELS
Syllabus
fundamentals of Quantum mechanics, Schrodinger wave equation, significance of psi
and psi2, particle in one dimensional box, molecular orbital theory- bonding in homo
and hetero nuclear diatomic molecules- energy level diagrams of O2 and CO, etc., pi-
molecular orbitals of butadiene and benzene, calculation of bond order.
Structure and Bonding Models
Fundamentals of quantum mechanics:
Quantum mechanics was developed independently by W. Heisenberg and E.
Schrodinger in1926 and won the Noble Prize.
Quantum mechanics is a theoretical science that deals with the study of the motions of
the microscopic objects that have both waved and particle nature.
Quantum mechanics based on three postulates
1. State function
2. Operator
3. Equations of motion

Plank’s Quantum Theory: It states that, the emission of radiation from a body is due to
the vibrations of the charged particles in the body.

The radiant energy is emitted or absorbed by a body not continuously, but in the form of
small packets of energy called Quanta. It is directly proportional to the frequency of
light.

E = hv

Where h is plank’s constant

h=6.625×10-34J.Secor6.625×10-27Erg.Sec

De Broglie’s Wave theory:

De Broglie proposed that, electron has both particle and wave nature.
h
λ=
mc

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Heisenberg’s Uncertainty Principle:

It states that, it is not possible to determine accurately the position and momentum of
electron simultaneously.
h
∆ x ×∆ p≥
4π

Where h is the Planck’s constant

m= mass of the particle

Δx=uncertainty in position

Δp=uncertainty in momentu
Note: Quantum mechanics give irrational values when compared to classical mechanics.
So, we consider classical mechanics only.
SCHRODINGER WAVE EQUATION
Classical mechanics (based on Newton’s laws of motion) could explain satisfactorily the
motion of all microscopic bodies e.g. a falling stone, motion of planets, etc., but failed to
explain the motion of microscopic particles like motion of electrons.
Erwin Schrodinger developed quantum mechanics or wave mechanics on the basis of
de-Broglie’s principle and Heisenberg’s principle called quantum mechanical model
explains the behavior of an electron in an atom in terms of Schrodinger wave equation:

∂2Ψ/∂x2+∂2Ψ/∂y2+∂2Ψ/∂z2+8π2m/h2 (E-V)Ψ = 0
Where, x,y,z = space coordinates
m = mass of the electron
h = plank’s constant
E = total energy of the electron
V = potential energy the electron
Significance of Ψ:
 Ψ = amplitude of the wave (wave function)
 Ψ is the wave function. It gives the amplitude of the electron wave.
 Ψ is expressed in terms of coordinates x, y & z.
 The wave function may have positive or negative value depending upon the
values of coordinates.

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  It contains all the information about the electron in an atom.

Significance of Ψ2:
 The main aim of Schrodinger equation is to give a solution for the probability
approach.
 When the equation is solved the wave function ψ may be positive or negative, but
probability must always be positive, and it cannot be negative. Thus, it is better to
use ψ2 in the favour of ψ.
 Hence the probability of finding the electron at a point in space is given by ψ2.
 ψ2 is directly proportional to electron density.
 ψ2 is probability function and always positive.
 If ψ2 is maximum, the probability of finding the electron is also maximum (95%).

PARTICLE IN ONE DIMENSIONAL BOX

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  Consider a particle which is restricted to move along x-direction x=0, x=a inside a
box bounded by infinitely rigid walls.
 The particle bounces back and forth between the walls of the box.
 The particle does not lose energy when it colloids with the walls so that its total
energy remains constant.

The potential inside the box V=0

The potential outside the box V=∞
For a system, such as an atom or a molecule whose energy does not change with time
than the Schrodinger wave equation is
Mathematically,
Ĥ Ψ = EΨ
Place the one dimensional Hamiltonian equation in above equation.
[-h2/8π2m ∂2/∂x2+ V] Ψ = EΨ
-h2Ψ/8π2m ∂2/∂x2+ VΨ = EΨ
-h2Ψ/8π2m ∂2/∂x2+ VΨ – EΨ = 0
∂2Ψ/∂x2+8π2m/h2 EΨ -8π2m/h2VΨ = 0
∂2Ψ/∂x2+8π2m/h2(E-V) = 0
The above equation is second order Schrodinger wave equation for a particle moving
along one dimension only.
Introduction to Molecular Orbital Theory
Atom:
 Atoms are the building blocks of all elements.
 These are indivisible particles.
 Atoms can neither be created nor destroyed in chemical reactions.

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  Atoms are composed of three fundamental particles like electrons, protons, &
neutrons.
 Protons have positive electrical charge, Neutrons have no electrical charge, and
Electrons have negative electrical charge.
 Protons and Neutrons are found together in the nucleus. Electrons revolve
around the nucleus.
 Electrons revolve around the nucleus in a fixed circular path called an Orbit. The
maximum number of electrons present in an Orbit is 2n2.
 Orbital is the area around the nucleus where the probability of finding an
electron is maximum. The maximum number of electrons present in an Orbital is
2.
Pauli’s Exclusion Principle:
 It states that no two electrons in an atom can have same values for all the four
quantum numbers.
 The electrons occupying the same orbital must have opposite spins.

Aufbau Principle:
 It states that electrons are filled into the atomic orbital in the increasing order of
their energies.
 Follow two rules 1) Filling takes place on the basis of lowest (n+l) values.
2) If same (n+i) value come take lowest n value

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Hund’s Rule:
 It states that each degenerate orbital should fill with one electron first and after
words pairing will takes place.

Chemical Bonding:
The force of attraction existing between two or more atoms that results in the formation
of stable molecules is called chemical bonding.
It includes various types of bonds like Ionic bond, Covalent bond, coordinate covalent or
dative bond.
Ionic bonds are formed by the transfer of electrons.
Covalent bonds are formed by the sharing of electrons.
Coordinate Covalent or dative bonds are complete transfer of electrons.
sigma bond pi bond
It is formed by the overlap of It is formed by the sidewise or lateral
orbitals along the axes. overlapping of orbitals.
It is stronger bond. It is weaker bond.

It is less reactive. It is more reactive.

It has independent existence. It exists along with the σ bond.

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Covalent bond in different molecules:
Single bond: A single bond contains only one σ bond. It is formed by sharing one pair of
electrons.
Ex: H-H
Double bond: A Double bond contains one σ bond and one π bond. It is formed by
sharing two electron pairs.
Ex: O=O
Triple bond: A Triple bond contains one σ bond and two π bonds. It is formed by
sharing three electron pairs.
Ex: N≡N
MOLECULAR ORBITAL (M.O) THEORY
 Molecular Orbital Theory was developed by Hund’s & Mulliken.
 Molecular orbitals are formed by the combination of atomic orbitals of
comparable energies and proper symmetry.
 An electron in Atomic orbital is influenced by one nucleus i.e., the Atomic orbital
is mono centric.
 Whereas the electrons in Molecular orbital are influenced by two or more nuclei
i.e., the Molecular orbital is polycentric.
 The number of Molecular orbitals formed is equal to the number of atomic
orbitals combined.
 When two atomic orbitals combine then two Molecular orbitals are formed. One
is bonding molecular orbital, and another is anti-bonding molecular orbital.
 The maximum capacity of M.O is two electrons with opposite spins.
 Molecular orbitals are filled according to Hund’s rule, Pauli’s Exclusion principle
and Aufbau principle.
 Atomic Orbitals are denoted as s, p, d… Whereas Molecular orbitals are denoted
as σ, π, δ…
 According to wave mechanics, the atomic orbitals can be expressed by wave
function Ψ (amplitude of the electrons wave by Schrodinger wave equation).
 It is very difficult to solve the wave equation for the molecules.

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  To overcome this problem, Linear Combination of Atomic Orbitals (LCAO)
method is introduced.
 This method is applied to Homo nuclear diatomic molecule like H2 molecule.
H2 molecule consists of two hydrogens A and B. The atomic orbitals may be
representing by wave function ΨA and ΨB.
Therefore, Bonding molecular orbitals and Antibonding molecular orbitals are
formed as
σ= ΨA + ΨB (Bonding M.O)
σ*= ΨA - ΨB (Anti Bonding M.O)

 Bonding M.O has less energy (more stable) and Anti-Bonding M.O has more
energy (less stable)

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  The order of energies of the orbitals is as follows.
Bonding Molecular Orbitals<Atomic Orbitals<Anti Bonding Molecular
Orbitals
 Filling of electrons in an atomic orbital takes place on the basis of Hund’s rule and
Afbau principle.
Important note:
 For the molecules having 14 electrons and below the electronic configuration is
σ 1s< σ* 1s< σ 2s<σ* 2s< [π2p x=π2p y]<σ2pz<[π*2p x=π*2p y]<σ*2pz
 For the molecules having 15 electrons and above the electronic configuration is

σ 1s< σ* 1s< σ 2s <σ* 2s <2p z<[π2p x= π2p y]< [π*2p x= π*2p y]<σ*2p

ENERGY LEVEL DIAGRAM FOR HOMO NUCLEAR DIATOMIC MOLECULE

Energy level diagram for O2 molecule:
 Oxygen atomic number -8
 Electronic configuration 1s22s22px4
 For oxygen molecule (O2) total 16 electrons
 Electronic configuration of O2molecule is
 σ 1s2 < σ* 1s2 < σ 2s2<σ*2s2<σ2p2z<[π2p2x=π2p2y]<[π*2p1x=π*2p1y]
 In O2 molecule configuration anti-bonding π,π* are unpaired electrons.So, O2
molecule is paramagnetic.

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 Bond order:
The no. of bonds that are present in a particular molecule is called bond order.
1
Bond order= ( Number of electrons∈ Bonding molecular orbitals−Number of electrons ∈ Anti bonding molecular orbital
2
Or
1
Bond Order= (N b −N a )
2
Where, Nb = Number of bonding electrons
Na = Number of anti- bonding electrons

Bond order for O2 Molecule:

 Number of electrons∈ Bonding molecular orbitals=10
 Number of electrons∈ Anti bonding molecular orbitals=6
1
Bond Order= (N b −N a )
2
1
Bond Order= (10−6)
2
4
Bond Order=
2

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 Bond Order=2
 The structure of O2 molecule is O=O

ENERGY LEVEL DIAGRAM FOR HETERO NUCLEAR DIATOMIC MOLECULE

Energy level diagram for CO molecule:
 Carbon atomic number -6, E.C - 1s2 2s2 2px2
 Oxygen atomic number -8, E.C - 1s2 2s2 2px4
 For carbon monoxide molecule (CO) total 14 electrons
 Electronic configuration of CO molecule is
 σ 1s2 < σ* 1s2 < σ 2s2<σ*2s2< [π2p2x=π2p2y]<σ2p2z
 In CO molecule configuration anti-bonding no unpaired electrons.So, CO molecule
is diamagnetic.

Bond order for CO Molecule:

 Number of electrons∈ Bonding molecular orbitals=10
 Number of electrons∈ Anti bonding molecular orbitals=4
1
Bond Order= (N b −N a )
2

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 1
Bond Order= (10−4)
2
6
Bond Order=
2
Bond Order=3
 The structure of CO molecule is C ≡ O

π - MOLECULAR ORBITAL DIAGRAMS

 The number of π molecular orbitals is equal to the number of atoms contributing

a p orbital to the π system.
 The lowest π molecular orbital will have zero vertical nodes. Each successive π
molecular orbital as energy increases will have one additional vertical node.
 The Highest Occupied Molecular Orbital (HOMO) is the highest energy π
molecular orbital that has electrons in it.
 The Lowest Unoccupied Molecular Orbital (LUMO) is the lowest energy π
molecular orbitalthat has no electrons in it.

π Molecular Orbitals of Ethylene

1. In ethylene, there are two adjacent carbon atoms involved in the π system and
the combination of a p orbital from each of these atoms will result in two π
molecular orbitals: π1 and π2*, (also referred to as ψ1 and ψ2*).

2. π1 is a bonding molecular orbitaland is the Highest Occupied Molecular Orbital

(HOMO).
3. π2* is an antibonding molecular orbital and is the Lowest Unoccupied Molecular
Orbital (LUMO).
4. The orbitals are arranged in the order of increasing energy.

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 5. The number of vertical nodes in a molecular orbital increase as the energy
increases.
6. π1 has zero vertical nodes and π2* has one vertical node.

π Molecular Orbitals of 1, 3 Butadiene

1. 1,3-butadiene is a conjugated system.

2. There are four adjacent carbon atoms involved in the π system and the
combination of a p orbital from each of these atoms will result in four π
molecular orbitals: π1, π2, π3*, and π4* (also referred to as ψ1, ψ2, ψ3*, and ψ4*).

3. π1and π2 are bonding molecular orbitals and π2 is the Highest Occupied Molecular
Orbital (HOMO).
4. π3* and π4* are antibonding molecular orbitals and π3*is the Lowest Unoccupied
Molecular Orbital (LUMO).
5. The orbitals are arranged in the order of increasing energy.

6. The number of vertical nodes in a molecular orbital increase as the energy

increases.
7. π1 has zero vertical nodes and they increase until π4* which has 3 vertical nodes.

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 π- Molecular Orbital of Benzene

1. Benzene has a planar hexagonal structure in which all the six carbon atoms are
sp2 hybridized. Four valence electrons of each carbonform three covalent bonds
with two carbon atoms and one hydrogen atom.

2. There are six adjacent carbon atoms involved in the π system and the
combination of a p orbital from each of these atoms will result in sixπ molecular
orbitals: π1, π2=π3, π4*=π5* and π6* (also referred to as ψ1, ψ2=ψ3, ψ4*=ψ5* and
ψ6*).
3. π1, π2andπ3 are bonding molecular orbital and π2=π3is the Highest Occupied
Molecular Orbital (HOMO).
4. π4*=π5* and π6*are anti- bonding molecular orbital and π4*=π5*is the Lowest
Unoccupied Molecular Orbital (LUMO).
5. The orbitals are arranged in the order of increasing energy.
6. The number of vertical nodes in a molecular orbital increase as the energy
increases.
7. π1 has zero vertical nodes and they increase until π6* which has 3 vertical nodes.
8. In benzene molecule, nodal planes formation can be explained in two different
ways i.e., through bonds and through atoms.

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Bond order:
The no. of bonds that present in a particular molecule is called bond order.
Bond order = ½ [Nb – Na]
Where, Nb = no. of bonding electrons
Na= no. of anti- bonding electrons
E.g. 1)For Hydrogen molecule single bond is present. H - H
2) For Oxygen molecule double bond is present. O = O
3)For Nitrogen molecule triple bond is present. N _=N

1) What is the bond order for N2 molecule?

A) Nitrogen atomic number 7 and 7 electrons are present in the atom.

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 So, N2 molecule contains 14 electrons.
Electronic configuration: σ 1s2 < σ* 1s2 < σ 2s2<σ*2s2< [π2p2x=π2p2y]<σ2p2z
We know that,
Bond order = ½ [Nb – Na]
Bond order = ½ [8– 4]
Bond order = ½ [6]
Bond order = 3
2) What is the bond order for H2 molecule?
A) Hydrogen atomic number 1 and 1 electron is present in the atom.
So, H2 molecule contains 2 electrons.
Electronic configuration : σ 1s2
we know that,
Bond order = ½ [Nb – Na]
Bond order = ½ [2- 0]
Bond order = ½ [2]
Bond order = 1
3) What is the bond order for NO molecule?
A) Nitrogen atomic number -7, E.C - 1s2 2s2 2p3
Oxygen atomic number -8, E.C - 1s2 2s2 2p4
For Nitrogen monoxide molecule (NO) total 15 electrons
Electronic configuration: σ 1s2<σ*1s2< σ 2s2<σ* 2s2<2p2z<[π2p2x= π2p2y]< [π*2p1x= π*2p y]
we know that,
Bond order = ½ [Nb – Na]
Bond order = ½ [10- 5]
Bond order = ½ [5]
Bond order = 2.
4) What is the bond order for NO+molecule?
A) Nitrogen atomic number -7, E.C - 1s2 2s2 2p3
Oxygen atomic number -8, E.C - 1s2 2s2 2p4
O+ means 7 electrons
For Nitrogen monoxide ion (NO+) total 14 electrons
Electronic configuration: σ 1s2 < σ* 1s2 < σ 2s2<σ*2s2< [π2p2x=π2p2y]<σ2p2z

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 we know that,
Bond order = ½ [Nb – Na]
Bond order = ½ [10- 4]
Bond order = ½ [6]
Bond order = 3
5) What is the bond order for NO- molecule?
A) Nitrogen atomic number -7, E.C - 1s2 2s2 2p3
Oxygen atomic number -8, E.C - 1s2 2s2 2p4
O- means 9 electrons
For Nitrogen monoxide ion (NO-) total 16 electrons
Electronic configuration:
σ 1s2 < σ* 1s2 < σ 2s2<σ*2s2<σ2p2z<[π2p2x=π2p2y]<[π*2p1x=π*2p1y]
We know that,
Bond order = ½ [Nb – Na]
Bond order = ½ [10– 6]
Bond order = ½ [4]
Bond order = 2
Easy way to find bond order of a molecule:

No. of Bond order

electrons
8 0
9 0.5
10 1.0
11 1.5
12 2.0
13 2.5
14 3
15 2.5
16 2.0
Question Bank 17 1.1
18 1.0
19 0.5
20 0
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 1. Write down the Schrodinger wave equation and explain the significance of terms
involved?
2. Explain about postulates of Molecular orbital theory?
3. Derive an equation for particle in a one-dimension box?
4. Draw molecular orbital diagram of homo nuclear diatomic molecule and calculate
its bond order?
5. Draw molecular orbital diagram of CO and calculate its bond order?
6. Draw molecular orbital diagram of 1,3 Butadiene molecule and calculate its bond
order?
7. Draw molecular orbital diagram of benzene and calculate its bond order?

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