CH-103-Physical Chemistry

Pravarthana Dhanapal
Email id: dpravarthana@iiti.ac.in

1
“The illiterate of the 21st century will not be those who
cannot read and write, but those who cannot learn, unlearn,
and relearn.”

― Alvin Toffler

"What you have learned is a mere handful; What you haven't

learned is the size of the world“

― Avaaiyar

2
 Course Syllabus
Linking microscopic and bulk thermodynamic properties:
Distribution of molecular states and relation to entropy,
Boltzmann distribution, ensembles, partition functions.

Elucidation of structure and properties: Experimental

techniques, Interaction light with matter, absorption and
emission spectra, intensities of spectral lines, Beer-
Lambert law, spontaneous and simulated emission,
transition moments and selection rules, Franck-Condon
principle, lasers and fluorescence.
Text Books
1. P.W. Atkins, J.D. Paula, Physical Chemistry, 9th Edn., Oxford University
Press, 2010, ISBN 13: 978-1-429-21812-2.

LRC: 3rd Floor, Book Shelf, 541 ATK.10 E, 536.7 GRE, 541.369 HIL, 536.5
ATT, and 536.7 LAU and 530.13. 3
 P.W. Atkins, J.D. Paula, Physical Chemistry, 9th
Edn
Linking microscopic and bulk thermodynamic properties:
Chapter 15 but Fundamental, Chapters (1,2,3) and minor
portions Chapters (7, 8, 17, and 20).

Elucidation of structure and properties: Chapter 12 and

13.

4
 Linking microscopic and bulk thermodynamic
properties.
Microscopic?
What is the basic constituent of microscopic?
Atoms: Nuclei (protons & neutrons) + Electrons
What governs the constituent of atoms?
Quantum Mechanics
Macroscopic?
What is the criterion to decide macroscopic?
Follows classical mechanics and thermodynamics

How to link microscopic to bulk thermodynamic properties?

Need to compute 6N variables and computationally
expensive.
What approach need to be employed to find the link?
5
 History of Atomic Models

 Ancient Greek Beliefs: Matter made up of atoms. This tiny units

differ in shape and size resulting in different properties.

 Dalton’s Atomic Theory (1808): definite particles called atom,

different elements different mass, and combine in definite
proportion.

 J.J. Thomson’s Theory (1904): negatively-charged electrons

embedded within a positively-charged.

 Rutherford’s Hypothesis (1911): the nucleus contains positively

charged particles called protons from the results of alpha particle
scattering by thin metal foil.

 Bohr’s Theory (1913): electrons travel in defined circular orbits

around the nucleus.
6
 Classical Particle Follow Definite Trajectory

 Classical mechanics describes the behavior of objects mainly by two equations

that total energy is constant in absence of external forces, the other expresses
the response of particles to the forces acting on them.

 Energy is capacity to do work, and it is conserved. The unit is joule (J).

 Total energy is sum of kinetic energy (motion) and potential energy (position,
depends on the type of interaction the body experiences).
𝑝2
𝐸= + 𝑉𝑃
2𝑚
Consider a particle free to move in x direction along 𝑉𝑃 =0
1 2
𝑑𝑥 2𝐸𝑘
=
𝑑𝑡 𝑚
1 2
2𝐸𝑘
So, 𝑥 𝑡 =𝑥 0 +𝑚 t
𝑚
𝑝 𝑡 = 2𝑚𝐸𝑘 1 2
Definite trajectory, or definite position and momentum at each instant
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 Classical Particle Can Have Arbitrary Energy
𝑑𝒑
Newton’s 2nd law of motion 𝑭=
𝑑𝑡
𝑑𝑥 2
𝐹=m
𝑑𝑡
If a particle of mass m is initially stationary and is subjected to a constant
force F for a time 𝜏, then its kinetic energy increases from zero to
𝐹2𝜏 2
𝐸𝑘 = Translational Motion
2𝑚
If a constant torque is applied for a time 𝜏, the rotational energy of an
initially stationary body
𝑇 2 𝜏 2 Rotational Motion
𝐸𝑘 =
2𝐼
1 2 Vibrational Motion
𝐸 = 𝑘𝐴
2
The solution implies that the energy of the particle of mass m
may be increased to any value
8
 Light is a Wave

The corpuscular theory:

Light is composed of very tiny, elastic and
rigid particles called corpuscules

May 1801: Thomas Young and the Nature of Light

https://www.aps.org/publications/apsnews/2008
05/physicshistory.cfm
https://royalsocietypublishing.org/doi/epdf/10
.1098/rstl.1804.0001
https://www.youtube.com/watch?v=DiSJspAVFh0
https://www.youtube.com/watch?v=0c0gvy_OOKc
https://www.youtube.com/watch?v=nuaHY5lj2AA
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Electromagnetic Wave
𝜈 1
𝜆𝜈 = 𝑐 𝜈= =
𝑐 𝜆

𝐸(𝑥, 𝑡) = 𝐸0 cos 2𝜋𝜈𝑡 − (2 𝜋 𝜆)𝑥 + 𝜙

𝐵(𝑥, 𝑡) = 𝐵0 cos 2𝜋𝜈𝑡 − (2 𝜋 𝜆)𝑥 + 𝜙

10
 Duality Nature of Light

Wave Particle

Photoelectric effect
Constructive

Destructive

Concepts of Modern Physics A. Beiser 11

 Wave-Like Character of Particles
Electron : Mass, Charge and Spin
French physicist Louis de Broglie in 1924, he suggested that any particle,
not only photons, travelling with a linear momentum p should have a
wavelength given by the de Broglie relation.

𝐸 = 𝑚𝑐 2
𝐸 = ℎ𝜈
𝜆𝜈 = 𝑐
ℎ
∴ 𝜆=
𝑝

https://www.youtube.com/watch?v=IYnU4T3jbgA
 1901 1905 1923
1900 onwards: Failure of classical mechanics, quantization, and realization of
wave-particle duality.
Visualize electron being wave and particle in atom,
molecule and crystal.
What questions arise to your mind?

1925 1926 1928 1948 13

 The Born interpretation of the wavefunction
 Wavefunction contains all the dynamical information about the system it
describes.
 Max Born pointed out wavefunction in analogy with wave theory of light gives the
information about location of the particle.
 Probability of finding a photon in the region proportional to square of amplitude
(intensity).

|Ψ|2 = Ψ ∗ Ψ if Ψ is complex |𝜳|𝟐 is positive

𝜳 is probability amplitude
|𝜳|𝟐 is probability density?
What is the unit of 𝜳 and |𝜳|𝟐 ?

𝑑𝜏 = 𝑑𝑥𝑑𝑦𝑑𝑧

|Ψ|2 𝑑𝜏

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 Normalization of the wavefunction

ℏ2 𝑑 2 Ψ
− 2
+ 𝑉(𝑥)Ψ = 𝐸Ψ
2𝑚 𝑑𝑥
 Ψ is solution, so N Ψ is solution, N is any constant.
 Normalization constant, N, facilitates the proportionality of the Born
interpretation (probability) becomes an equality over all space.

∞ 𝟏𝑫 𝟑𝑫
Ψ ∗ Ψ𝑑𝑥 =1 Ψ ∗ Ψ 𝑑𝜏 = 1 is 𝜳 square integrable?
−∞
𝑺𝒑𝒉𝒆𝒓𝒊𝒄𝒂𝒍 𝒄𝒐𝒐𝒓𝒅𝒊𝒏𝒂𝒕𝒆

∞ 𝜋 2𝜋
Ψ ∗ Ψ𝑟 2 sin 𝜃𝑑𝑟𝑑𝜃𝑑𝜙 = 1
0 0 0

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 Quantization of the wavefunction

 Ψ being infinity is not physically unacceptable. If infinity not square integrable.

 Ψ must be single-valued as it is absurd to have more than one probability that a
particle is at the same point.
 The 2nd derivative of Ψ must be well-defined if the equation is to be applicable
everywhere. Thus 1st derivative, its slope, is continuous
 𝜳 must be continuous, have a continuous slope, be single-valued, and be
square-integrable.

𝐄𝐱𝐜𝐞𝐩𝐭𝐢𝐨𝐧 𝐭𝐨 slope of the Ψ need not be continuous if the potential energy becomes infinite.
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 Information in a wave function
ℏ2 𝑑 2 Ψ
− = 𝐸Ψ Schrödinger equation
2𝑚 𝑑𝑥 2
𝑘 2 ℏ2 𝑝2
𝐸= =
Ψ = 𝐴𝑒 𝑖𝑘𝑥 + 𝐵𝑒 −𝑖𝑘𝑥 2𝑚 2𝑚

 Probability Density.
Ψ = 𝐴𝑒 𝑖𝑘𝑥 + 𝐴𝑒 −𝑖𝑘𝑥 = 2𝐴 cos 𝑘𝑥
|Ψ|2 =4|𝐴|2 cos 2 𝑘𝑥
 Operators, eigenvalues, and eigenfunctions.
𝐻Ψ = 𝐸Ψ Hamiltonian operator
ΩΨ = 𝜔Ψ Eigenvalue equation
(Observable Operator) 𝛹 =(Observable value)× 𝛹
∗
 Hermitian operators.
Ψ𝑖∗ ΩΨ𝑗 𝑑𝑥 = Ψ𝑗∗ ΩΨ𝑖 𝑑𝑥 = Eigenvalue
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 The uncertainty principle

 Heisenberg uncertainty principle: It is impossible to specify simultaneously, with

arbitrary precision, both the momentum and the position of a particle.
Schrödinger equation Solution to differential equation
𝑘 2 ℏ2 𝑝2
ℏ2 𝑑 2 Ψ
− = 𝐸Ψ Ψ= 𝐴𝑒 𝑖𝑘𝑥 + 𝐵𝑒 −𝑖𝑘𝑥 𝐸 = =
2𝑚 𝑑𝑥 2 2𝑚 2𝑚
𝐹𝑜𝑟 𝐵 = 0
ℏ 𝑑Ψ ℏ 𝑑𝑒 𝑖𝑘𝑥 ℏ
𝑝𝑥 Ψ = = 𝐴 = 𝐴 × 𝑖𝑘𝑒 𝑖𝑘𝑥 = 𝑘ℏΨ ∴ 𝑝𝑥 = ℏ𝑘
𝑖 𝑑𝑥 𝑖 𝑑𝑥 𝑖 Finite value
𝑥Ψ = 𝑥 × 𝐴𝑒 𝑖𝑘𝑥 Not defined
This principle is based on the wave-particle duality of matter.

Fundamental feature of quantum mechanics

https://www.scientificamerican.com/article/common-interpretation-of-heisenbergs-uncertainty-principle-is-proven-false/

https://www.aps.org/publications/apsnews/200802/physicshistory.cfm
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 Root mean square deviations
1
∆𝑝∆𝑥 ≥ ℏ
2
 Δp is uncertainty in linear momentum parallel to x-axis, while Δx is uncertainty
in position along that axis.
𝑛 𝑛
2
1 2 1
(∆𝑥) = 𝑥𝑖 − 𝑥 Where, 𝑥 = 𝑥𝑖 = 𝑥
𝑛 𝑛
𝑖=1 𝑖=1
∆𝑥 = ⟨𝑥 2 ⟩ − 𝑥 2 1 2
∆𝑝 = ⟨𝑝2 ⟩ − 𝑝 2 1 2

Expectation value Ω = Ψ ∗ ΩΨ 𝑑𝜏 ΩΨ = 𝜔Ψ

If ∆𝑥 = 0 then ∆𝑝 = ∞ To satisfy
1
If ∆𝑝 = 0 then ∆𝑥 = ∞ ∆𝑝∆𝑥 ≥ 2 ℏ

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 Free Particle Schrödinger Equation Solution

Translational motion

Consider a particle free to move in x direction along 𝑉𝑃 =0

ℏ2 𝑑 2 Ψ
− = 𝐸Ψ Schrödinger equation 𝐻Ψ = 𝐸Ψ
2𝑚 𝑑𝑥 2
.
Solution to above differential equation
𝑘 2 ℏ2
Ψ𝑘 = 𝐴𝑒 𝑖𝑘𝑥 + 𝐵𝑒 −𝑖𝑘𝑥 𝐸𝑘 = Index k ?
2𝑚
No restrictions on values of k, and therefore all values of the energy, are permitted.
Translational energy of a free particle is not quantized.

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 A particle in a box confined 1D
Particle with a mass m confined in a box of length L.
0, 0<𝑥<𝐿 1D-Confinement
𝑉 𝑥 =
∞, 𝑥 ≤ 0, 𝑥 ≥ 𝐿

Ψ𝑘 = 𝐴𝑒 𝑖𝑘𝑥 + 𝐵𝑒 −𝑖𝑘𝑥
= 𝐴(cos 𝑘𝑥 + 𝑖 sin 𝑘𝑥) + 𝐵 (cos 𝑘𝑥 − 𝑖 sin 𝑘𝑥)
= 𝐶 cos 𝑘𝑥 + 𝐷 sin 𝑘𝑥
Applying boundary condition
Ψ𝑘 𝑥 = 0, 𝑥 ≤ 0, 𝑥 ≥ 𝐿 Physically impossible for the particle to be
found with an infinite potential energy.
Ψ𝑘 0 = 𝐶 Implies 𝐶 =0 ∴ Ψ𝑘 𝑥 = 𝐷 sin 𝑘𝑥
Ψ𝑘 𝐿 = 0 Taking 𝐷 = 0 conflicts Born interpretation as Ψ𝑘 𝑥 = 0 ∀ 𝑥
sin 𝑘𝐿 = 0 Implies 𝑘𝐿 = 𝑛𝜋 𝑛 = 1,2, …
Ψ𝑛 𝑥 = 𝐷 sin(𝑛𝜋𝑥 𝐿) 𝐸𝑛 = 𝑛2 ℎ2 8𝑚 𝐿2 Quantized
21
 Particle in a Box

𝐸 = ℎ𝜈
22
𝐿𝑦 1
=
𝐿𝑥 1

23
𝐿𝑦 1
=
𝐿𝑥 1

24
𝐿𝑦 1
=
𝐿𝑥 1

25
𝐿𝑦 1
=
𝐿𝑥 1

26
𝐿𝑦 1
=
𝐿𝑥 1

27
𝐿𝑦 1
=
𝐿𝑥 1

28
 The energy of a molecule, atom, or subatomic particle that is confined to a
region of space is quantized, or restricted to certain discrete energy values.

 What happens to quantization for particles with large mass or large container?
𝐸𝑛 = 𝑛2 ℎ2 8𝑚 𝐿2
 Consequently, quantization is very important for electrons in atoms and
molecules, but usually unimportant for macroscopic bodies.
0.01 kJ mol-1 10 kJ mol-1 103 kJ mol-1

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Thank You

30
 Black-body Radiation

 Black-body: Ideal EM wave absorber and emitter.

 Why hot black-body emits radiation?
 Distribution in energy levels due to thermal contact with the surroundings. So, to
reach thermal equilibrium it comes to ground state from excited state by emitting
EM wave.

Thermal equilibrium in pinhole Energy Distribution in Black-body cavity

31
Failure of classical mechanics based Rayleigh–Jeans law for
explanation of black-body radiation.
 Rayleigh considered electromagnetic field as oscillators of all frequencies.
When a high frequency, short wavelength
oscillator (a) is excited, that frequency of
radiation is present.

The presence of low frequency, long wavelength

radiation (b) signifies that an oscillator of the
corresponding frequency has been excited.
From equipartition principle to calculate the
average energy of each oscillator as kT.

Energy density The equation predicts that oscillators

of very short wavelength (ultraviolet
𝑑𝐸 = 𝜌𝑑𝜆 radiation, X-rays, and even γ-rays)
Density of states are strongly excited even at room
temperature.
8𝜋𝑘𝑇 Ultraviolet catastrophe
𝜌= 4
𝜆 Classical physics predicts cool objects
should glow in the dark 32
 Planck distribution
Thermal equilibrium in pinhole Exchange of energy between modes (Photon)
and particles or oscillators.

The probability that a single mode has energy

𝐸𝑛 = 𝑛ℎ𝜈 is given by the usual Boltzmann
distribution

𝑁𝑖 𝑒 −𝛽ε𝑖
= 𝑝𝑖 = −𝛽ε𝑖
𝑁 𝒊𝑒
𝐸𝑛
−𝑘𝑇
𝑒 Probability that the state contains
𝑝𝑛 =
∞
𝐸
− 𝑛 𝑛 photons of frequency 𝜈
𝑛=0 𝑒
𝑘𝑇

∞ 𝐸𝑛 𝑛ℎ𝑣
Mean energy of the mode of ∞
𝑛=0 𝐸𝑛 𝑒
−𝑘𝑇 ∞
𝑛=0 𝑛ℎ𝑣 𝑒
− 𝑘𝑇

frequency 𝜈 𝐸= 𝐸𝑛 𝑝𝑛 = 𝐸𝑛
−𝑘𝑇
= 𝑛ℎ𝑣
− 𝑘𝑇
∞ ∞
𝑛=0 𝑛=0 𝑒 𝑛=0 𝑒

ℎ𝑣
𝐸= ℎ𝑣
𝑒 𝑘𝑇 −1
33
https://edisciplinas.usp.br/pluginfile.php/48089/course/section/16461/qsp_chapter10-plank.pdf
 The Planck distribution explains black-body radiation

𝐸 = 𝑛ℎ𝜈 𝑛 = 0, 1, 2, …

ℎ = 6.626 × 10−34 𝐽 𝑠
𝑑𝐸 = 𝜌𝑑𝜆
8𝜋ℎ𝑐
𝜌 = 5 ℎ𝑐 𝜆𝑘𝑇
𝜆 (𝑒 −1)

Shorter wavelenghth Longer wavelenghth

ℎ𝑐 ∕ 𝜆𝑘𝑇 ≫ 1 ℎ𝑐 ∕ 𝜆𝑘𝑇 ≪ 1
ℎ𝑐 8𝜋𝑘𝑇
𝑒 ℎ𝑐 𝜆𝑘𝑇 → ∞ 𝑒 ℎ𝑐 𝜆𝑘𝑇 →1+ 𝜌= 4
𝜆
𝜆𝑘𝑇
𝜌→0 1 2
𝑒𝑥 = 1 + 𝑥 + 𝑥 +⋯
∵ 2
𝑒 𝑥 = 1 + 𝑥 𝑓𝑜𝑟 𝑥 ≪ 1

34
 Wave-Particle Duality
 Energies of EM wave and atoms are quantized, which explains well the
experimental data unlike classical physics.
 Experimental evidence of particle nature that exhibited as wave nature by
classical physics. Similarly evidence of wave nature that exhibited as particle
nature by classical physics.
The particle character of electromagnetic radiation

𝐸 = 𝑛ℎ𝜈 𝑛 = 0, 1, 2, … ℎ = 6.626 × 10−34 𝐽 𝑠

0, ℎ𝜈, 2ℎ𝜈, 3ℎ𝜈, … It can be considered each particle having an energy hν

These particles of electromagnetic

radiation are now called photons.

Discrete spectra of atoms or molecules

can be pictured as generating a photon
of energy hν when it discards an energy
of magnitude ∆E.

35
 Evidence of Particle-Like Character of Radiation
 The measurement of the energies of electrons produced in the photoelectric
effect. The particle character of electromagnetic radiation
1
𝑚𝑒 𝑣 2 = ℎ𝜈 − 𝜙
2

What is the slope and x intercept? 36

 Evidence of Wave-Like Character of Particles

American physicists Clinton Davisson and Lester Germer in 1927, who observed the
diffraction of electrons by Ni crystal.

https://journals.aps.org/pr/pdf/10.1103/PhysR
ev.30.705
Concepts of Modern Physics A. Beiser 37
 Electron Diffraction from Crystal

Crystal Electron Wavelength

h

2meV 1/ 2
Energy = 54 eV

𝜆 =0.166 nm
𝜃 = 65°
Bragg’s Diffraction
2𝑑 sin 𝜃 = n𝜆
𝑑 =0.091 nm
𝜆 =0.165 nm

Concepts of Modern Physics A. Beiser 38