UNIT-3

Structure and Bonding Models

Quantum Mechanics:-
It is the branch of physics which explains about the motion of microscopic particles like electrons, protons etc. It was
introduced by Max Planck in 1900.

Waves & particles:

Wave:- A wave is nothing but spreading of disturbance in a medium. The
Characteristics/properties of waves are 1) Amplitude 2) Time period 3) Frequency 4) Wavelength
5) Phase 6) Intensity.

Particle:- A particle is a point in space which has mass & occupies space or region. The characteristics/properties of a
particle are 1) Mass 2) velocity 3) Momentum 4) Energy etc.

1.Explain De-broglie-Hypothesis and properties De-broglie-waves.

Matter Waves or De-broglie-waves Or De-broglie-Hypothesis

In 1924 Lewis de-Broglie proposed that “like radiation, matter also has dual nature”.

According to his hypothesis, a moving particle (electron, proton, and neutron) has wave property
associated with it. The waves associated with moving particles are called as matter waves or pilot waves or
de-Broglie waves.

The wavelength of such a wave is given as,

𝒉 𝒉
𝜆= =
𝒎𝒗 𝒑
Where ‘m’ is the mass of the particle, ’p’ is momentum.

Expressions For de-Broglie Wavelength(λ)

According to Planck‟s quantum theory, the energy of a photon is given by,

𝒉𝒄
E = h𝜈 = ----- (1)
𝛌
h- planck’s constant, 𝜈-frequency of photon

According to Einstein mass energy relation

E = mc2 ----- (2)
m-mass of a photon, c-velocity of light

From equation of (1) & (2)

𝒉𝒄
= mc2
𝛌

𝒉
𝜆 = 𝒎𝑪
If we consider the case of a material particle of mass ‘m’ moving with velocity ‘v’, then

𝒉 𝒉
𝜆 = 𝒎𝒗 = 𝒑

The above expression is for de-broglie wave-length(λ).

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Properties or characteristics of matter waves or de-broglie waves:-
 Lesser the mass of the particle, greater is the wavelength associated with it.
 Smaller the velocity of the particle, longer is the wav-length associated with theparticle.
 When V = 0, 𝜆 = ∞ & 𝑉 = ∞, 𝜆 = 0.
 Matter waves produced when the particles in motion are charged or uncharged.
 Matter wave are not electro-magnetic waves.
 Matter waves travel faster than the velocity of light.
 Wave nature of matter gives an uncertainty in the position of the particle.

2.Explain Heisenberg uncertainty principle.

Heisenberg uncertainty principle:-

In 1927, Heisenberg proposed a very interesting principle known as uncertainty principle, which states that
“it is impossible to determine both the exact position and exact momentum of a moving particle at the
same time”.

“If ′Δx′& ′Δp′ are uncertainties in the measurement of position & momentum of the particle then mathematically this
uncertainties of this physical variables is written as
𝐡
Δx.Δp ≥ ----- (1)
𝟒𝛑
Explanation:-
(i) If ∆x = 0. i.e., the position of a particle is measured accurately, then from eq-(1).
𝐡
Δp =
𝚫𝐱.𝟒𝛑

𝐡
Δp = = 0
∞

It means that, the momentum of the particle can’t be measured.

(ii) If ∆p = 0. i. e., the momentum of a particle is measured accurately, from eq. (1).
𝐡
Δx =
𝚫𝐩.𝟒𝛑

𝐡
Δx = = 0
∞

From the above said observations made by Heisenberg, he clearly states that it is impossible to design an
experiment to prove the wave & particle nature of matter at any given instant of time.
If one measures position or momentum accurately, then there will be an uncertainty in the other. Thus, the
Heisenberg’s uncertainty principle gives the probability of determining the particle at any given instant of
time in place of certainty.

Applications:-
• It explains the non-existence of e’s in the nucleus.
• It gives the binding energy of an e’s in atom.
• It calculates the radius of Bohr’s first orbit.

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3.Derive the expression for Schrodinger’s Wave Equation and the Physical significance of significance of ψ and ψ2
Schrodinger’s Wave Equation:-
Schrodinger’s describes the wave nature of a particle in mathematical form and is known as Schrodinger wave equation
(SWE). Schrodinger’s wave equation which calculates the probability of finding an electron at various point in an atom.
Let us consider an electron (particle) moving along a positive direction along the axes . Let x,y,z be the coordinates of
the particle &′ψ′ is the wave-displacement or wave-function of the matter wave at any time ’t’.
We can express the classical differential wave equation of the material particle in three- dimension axes is given as
∂2Ψ ∂2 Ψ ∂2 Ψ 8𝜋2 m
+ ∂𝑦 2 + + (𝐸 − 𝑉) Ψ = 0
∂𝑥 2 ∂𝑧 2 ℎ2

Schrodinger’s wave equation can be derived as follows

𝒙
Ψ = A sin 2𝜋 𝛌 ……… (1)
Where Ψ=amplitude of wave (called wave function)
𝑥= the displacement in a given direction
λ = wave length
A = constant

By differentiating eq(1) twice with respect to ′𝑥’

∂Ψ 2𝜋 𝑥
=A cos 2𝜋 λ ……… (2)
∂𝑥 λ

∂2Ψ −4𝜋2 𝑥
=A sin 2𝜋 λ …… (3)
∂𝑥 2 λ2

𝑥
But A sin 2𝜋 λ = Ψ

∂2 Ψ −4𝜋2
= Ψ …… (4)
∂𝑥 2 λ2

The kinetic energy of the particle with mass ‘m’ and velocity ‘v’ is given by the relation

1 1 𝑚 2𝑣 2
K.E = 𝑚𝑣 2 = ……. (5)
2 2 𝑚

According to De broglie equation

ℎ
𝜆 = 𝑚𝑣

ℎ2
𝜆2 = 𝑚 2 𝑣 2

ℎ2
𝑚2 𝑣 2 = λ2
Substituting the value of 𝑚 2 𝑣 2 in eq (5), we get
1 ℎ2
K.E = = …….(6)
2 𝑚𝛌𝟐
From the eq (4) we have
∂2 Ψ −4𝜋 2
= 2 Ψ
∂𝑥 2 λ
−4𝜋 2Ψ
λ𝟐 = ∂2 Ψ
….. (7)
∂𝑥2

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 ′
Substituting the value of ‘λ2 in eq (6), we get
−1 ℎ2 ∂2 Ψ
K.E = 2𝑚 4𝜋2 𝛹 ∂𝑥 2

−ℎ 2 ∂2 Ψ
K.E= 8𝜋2 𝑚𝛹 ∂𝑥 2

If E and V are the total energy and potential energy of the particle respectively, then

E=K.E+P.E

E=K.E+V

(E─V) = K.E

−ℎ 2 ∂2 Ψ
(E─V)= 8𝜋2𝑚𝛹 ∂𝑥 2

∂2Ψ −8𝜋2 𝑚
= (E─V) Ψ
∂𝑥 2 ℎ2

∂2Ψ −8𝜋2 𝑚
+ (E─V) Ψ = 0
∂𝑥 2 ℎ2

This is called Schrodinger’s wave equation in one dimension.

It need to be generalized a particle whose motion is described by three coordinates x, y, z in space. Thus
𝛛𝟐 𝚿 𝛛𝟐 𝚿 𝛛𝟐 𝚿 𝟖𝝅𝟐 𝐦
+ 𝛛𝒚𝟐 + + (𝑬 − 𝑽) 𝚿 = 0
𝛛𝒙𝟐 𝛛𝒛𝟐 𝒉𝟐

∂2 ∂2 ∂2
+ ∂𝑦 2 + ∂𝑧 2 is represented as Δ2
∂𝑥 2

The Schrodinger’s wave equation can be written as

𝟖𝝅𝟐𝐦
Δ2 𝚿 + (𝑬 − 𝑽) 𝚿 = 0
𝒉𝟐
2
Δ Laplacian operator.

Physical significance of significance of ψ and ψ2

The wave function ψ or Eigen-function (𝛙) was introduced by Erwin Schrödinger to explain the properties of the matter
waves.
• ψ is a wave function and refers to the amplitude of electron wave i.e. probability amplitude. It has got no
physical significance. The wave function ψ may be positive, negative or imaginary.
 [ψ]2 is known as probability density and determines the probability of finding an electron at a point within
the atom.
• This means if
[ψ]2 is zero, the probability of finding an electron at that point is negligible.
[ψ]2 is high, the probability of finding an electron is high i.e. electron is present at that place for a long time.
[ψ]2 is low. The probability of finding an electron is low i.e. electron is present at that place for a shorter time.

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4.Explain Molecular orbital theory.

Molecular Orbital Theory:

The molecular orbital theory (MOT) was developed by F. Hund and R. S. Mulliken to describe the structure and
properties of different molecules.

Features of the molecular orbital theory;:

1. The atomic orbitals overlap to form new orbitals called molecular orbitals.
2. Only those atomic orbitals can combine to form molecular orbitals which have comparable energies and proper
orientation.
for example 1S combine with 1S.
3. The number of molecular orbitals formed is equal to number of atomic orbitals combined
4. When two atomic orbitals combined two new molecular orbitals called bonding molecular orbitals and anti-
bonding molecular orbitals.
5. Bonding molecular orbitals are formed by the combination of + and + part and – with ─ part of the electron
waves whereas anti- bonding molecular orbitals are formed by the combination of + with ─ part.
6. The bonding molecular orbitals have lower energy and hence greater stability than the corresponding anti-
bonding molecular orbitals.
7. The bonding molecular orbitals are represented by σ, π, δ. The anti-bonding molecular orbitals are represented
by σ∗, π∗, δ∗.
8. The electrons are filled into molecular orbitals in the increasing order of orbital energy (from the orbital with the
lowest energy to the orbital with the highest energy).
9. The probability of finding the electrons in the bonding molecular orbitals increases whereas it decreases in the
anti-bonding molecular orbital.
10. There is a nodal plane between the two nuclei of an anti-bonding molecular orbital. i.e a plane on which
electron density is zero.
11. The relative energies of molecular orbitals are found to be in increasing order as follows
σ(1s)<σ∗(1s)<σ(2s)<σ∗(2s)<[π(2px) π(2py)]<σ(2pz)<[π∗(2px) π∗(2py)]<σ∗(2pz)

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5.Explain molecular orbital configuration,magnetic properties and bond order for H 2, N2, O2,and CO
1. Molecular orbital diagram of H2 molecule:

• Combining the 1s orbitals of each hydrogen atom, two molecular orbitals are generated σ1s and σ*1s
• The σ1s orbital is generated by a constructive interference, where the two atomic orbitals wave functions add to
each other. This is the lower energy of the molecular orbital and is known as the bonding molecular orbital.
• The σ*1s orbital is generated by a destructive interference, where the wave functions of the two atomic orbitals
cancel each other. This is the higher energy of the molecular orbital and is known as an anti-bonding molecular
orbital σ∗1s.
• The lowest energy MO is bonding with electron density concentrated between two H atoms. The higher energy
MO is anti-bonding with electron density concentrated behind each H nucleus.

Given element – hydrogen

Atomic number of hydrogen – 1
Electronic configuration – 1s1
Total number of electrons in hydrogen molecule – 2

The molecular electronic configuration of H2-is σ1s2

Molecular orbital diagram of H2 is as follows:

Bond order

The bond order is calculated by subtracting the number of electrons in anti-bonding molecular orbitals (Nb) (from the
number of electrons in bonding molecular orbitals (Na) and dividing the difference by 2.
(𝐍𝐛−𝐍𝐚)
Bond order =
𝟐
𝟐−𝟎
Hence, the bond order of hydrogen molecules is =1
𝟐
 Magnetic property :
In H2 molecule, no unpaired electron is present hence H2 molecule is diamagnetic.

2. Molecular orbital diagram of N2 molecule:

Given element – Nitrogen

Atomic number of nitrogen – 7
Electronic configuration – 1s²2s²2p³
Total number of electrons in nitrogen molecule – 14

The molecular electronic configuration of N2-is

σ1s2, σ*1s2 , σ2s2 , σ*2s2, π2px2 , π2py2, σ2pz2

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Molecular orbital diagram of N2 is as follows:

 Bond order:

From the diagram it is clear that there are four fully filled bonding molecular orbitals and one completely filled anti-
bonding molecular orbital.
The bond order is calculated by subtracting the number of electrons in anti-bonding molecular orbitals (Nb) from the
number of electrons in bonding molecular orbitals (Na) and dividing the difference by 2.
(𝐍𝐛−𝐍𝐚)
Bond order =
𝟐
The total number of electrons present in the N2 molecule is 14.
Number of electrons in bonding orbitals: 8
Number of electrons in anti-bonding orbitals: 2
𝟏𝟎−𝟒
Hence, the bond order of nitrogen molecules is =3
𝟐
Bond order = 3.
The bond order is 3 which mean it has a triple bond and hence it has high bond strength.
 Magnetic property:
There are no unpaired electrons present. Hence it is diamagnetic.

3. Molecular orbital diagram of O2 molecule:

Given element – Oxygen

Atomic number of oxygen – 8
Electronic configuration – 1s²2s²2p4
Total number of electrons in nitrogen molecule – 16

The molecular electronic configuration of O2-is

σ1s2, σ*1s2 , σ2s2 , σ*2s2, π2py2 , π2pz2, σ2px2 , π∗2px1, π∗2py1

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Molecular orbital diagram of O2 is as follows:

Bond order:

From the diagram it is clear that there are four fully filled bonding molecular orbitals and one completely filled anti-
bonding molecular orbital.
The bond order is calculated by subtracting the number of electrons in anti-bonding molecular orbitals (Nb) from the
number of electrons in bonding molecular orbitals (Na) and dividing the difference by 2.
(𝐍𝐛−𝐍𝐚)
Bond order =
𝟐
The total number of electrons present in the O2 molecule is 16.
Number of electrons in bonding orbitals: 10
Number of electrons in anti-bonding orbitals: 6
𝟏𝟎−𝟔
Hence, the bond order of nitrogen molecules is 𝟐 = 2
Bond order = 2.
The bond order is 2 which mean it has a double bond.
 Magnetic property:
The presences of unpaired electrons show that O2 is paramagnetic.

4. Molecular orbital diagram of CO molecule:

Given elements – Carbon and Oxygen

Atomic number of carbon – 6
Atomic number of oxygen – 8
Electronic configuration of C – 1s²2s²2p2
Electronic configuration of O – 1s²2s²2p4
Total number of electrons in CO molecule – 14

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The molecular electronic configuration of CO-is

σ1s2, σ*1s2 , σ2s2 , σ*2s2, π2px2 , π2py2, σ2pz2

Molecular orbital diagram of O2 is as follows:

 Bond order:

From the diagram it is clear that there are four fully filled bonding molecular orbitals and one completely filled anti-
bonding molecular orbital.
The bond order is calculated by subtracting the number of electrons in anti-bonding molecular orbitals (Nb) from the
number of electrons in bonding molecular orbitals (Na) and dividing the difference by 2.
(𝐍𝐛−𝐍𝐚)
Bond order =
𝟐
The total number of electrons present in the CO molecule is 14.
Number of electrons in bonding orbitals: 10
Number of electrons in anti-bonding orbitals: 6
𝟏𝟎−𝟒
Hence, the bond order of nitrogen molecules is 𝟐 = 3
Bond order = 2.
The bond order is 3 which mean it has a triple bond.

 Magnetic property:
The CO molecule has no unpaired electrons, hence it is diamagnetic.