CH107: Physical Chemistry

• Quantum Mechanics in Chemistry:

Hydrogen atom: orbitals
Multielectron atoms: Spin orbital
Molecules: Molecular orbitals
• Molecular Spectroscopy: Rotation, Vibration, Raman

Instructor (D3):

Shobhna Kapoor, Ph.D

Room 15
1st floor, Physics Department
Phone: x-7161; 8878735161

Email: shobhnakapoor@chem.iitb.ac.in
 CH 107 2018 Course Information

Classes on Mondays (9:30 am), Tuesday (10:30 am)

and Thursdays (11:30 am)

Tutorials on Thursdays 8:30 am

Attendance, marks change and course related issues:

Course Secretary: Ms. Charine

Central Facility, Chemistry Department

Email: charine@chem.iitb.ac.in
Phone: (022)2576 4159
 CH 107: Division 3

Tutorial venue and Teaching Assistants

Thursdays: 8:30 – 9:30 am

D3/T1 LT-301 -Kailasham Ramalingam

D3/T2 LT-302 -Bala Maddala

D3/T3 LT-303 Shobhna Kapoor

UG TA
D3/T4 LT-202 -G. N. Patwari Pranjal

D3/T5 LT-203 -Pooja

Emails and phone numbers to be provided

Help sessions: Please send an email and schedule an appointment

 CH 107 schedule and evaluation scheme

Duration Half-semester (~8 weeks)

Quiz 13 October 2017

End-Semester Exam to be declared

Evaluation Scheme

Mini quiz during tutorials 8 Marks

Quiz 18 Marks

End-Semester Exam 24 Marks

Passing Marks ?
 Why should you study
Physical Chemistry?
Use the laws of physics and apply to chemistry
Deeper understanding of physical processes/mechanisms
and get insights on how things work the way they do!
Bridge between novel molecules (materials) prepared by
synthetic chemists and their potential applications.

https://www.acs.org/content/acs/en/careers/college-to-
career/areas-of-chemistry/physical-chemistry.html

• Biotechnology and healthcare

• Energy Science – “Solar Energy” conversion
• Wall Street, Law Firms and Venture Capitals
• Nanoelectronics/Nanotechnology: Molecular Electronics
 Relevance of CH107?
CH-107

Apply QM principles to
understand the behavior
of atoms and molecules

PH-107 CH-105
Dynamics of electrons Deeper/better Collective behavior of
and protons governed by understanding atoms and molecules
laws of quantum physics
of physical
processes

• You probably “know” what the end-results is…

• But not necessarily understand the reason “why?”
• The focus of CH107 is to understand: Why and
How…
 Contextual perspective
applied
Fundamentals of
PH-107 Quantum Physics
to the
Hydrogen
CH-107
Yields
Atom three

Quantum
Schrodinger numbers
Equation

Multi-electron Atoms
(Periodic Table)
Tunneling Particle Harmonic
Processes In a Box oscillator

Atomic/Molecular
Spectroscopy
Multi-atomic
Band theory Bonding, Molecular
Barrier Structure
Penetration

Chemical Reactions Intermolecular Forces

Biology, (Nano) And Interactions
Molecular Dynamics
Materials Science
Condensed Matter
Physics
 Outline of this course (16 x 1hr)
• Origin of Quantization ~2 lectures
Postulates of Quantum Mechanics
Particle in a Potential Well

• Electronic Structure in Atoms ~4 lectures

Hydrogen atom
Multi-electronic atoms

• Chemical Bonding ~4 lectures

Molecular Orbital Theory
Energetics/Electronic structure of homonuclear diatomics

• Molecular-Electronic Structure ~2-3 lectures

Heteronuclear diatomics and polyatomics, hybridization

• Molecular Spectroscopy ~2-3 lectures

QM in action – experimental verification of QM principles
 CH 107: Text books

• Physical Chemistry – I.N. Levine, 5th Ed.

• Physical Chemistry – P.W. Atkins 2nd Ed.
• Physical Chemistry: Molecular Approach - McQuarrie and Simon
• Fundamentals of molecular spectroscopy – Banwell and McCash

Important Websites:

CH107 Course Material for 2013 and previous year’s power-point slides:
www.chem.iitb.ac.in/academics/menu.php

http://vod.cdeep.iitb.ac.in/ (Previous years lectures)

All materials will be uploaded on IITB Moodle

http://moodle.iitb.ac.in
PH107: Recapitulation
 Atomic Spectra

Balmer Series The Rydberg-Ritz Combination

Principle states that the spectral lines
410.1 nm of any element include frequencies
 
434.0 nm 1  R  12  12  that are either the sum or the
486.1 nm   n1 n2  difference of the frequencies of two
656.2 nm R  1.09678 x 107 m 1 other lines.

“R∞ is the most accurately measured fundamental physical constant”

 Rutherford Model of Atom

Planetary model of atoms with Classical electrodynamics predicts that

central positively charged nucleus such an arrangement emits radiation
and electrons going around continuously and is unstable
 Bohr Phenomenological Model of Atom

Electrons rotate in circular orbits around a central (massive) nucleus, and

obeys the laws of classical mechanics.
Allowed orbits are those for which the electron’s angular momentum
equals an integral multiple of h/2π i.e. mevr = nh/2π
Energy of H-atom can only take certain discrete values: “Stationary States”
The Atom in a stationary state does not emit electromagnetic radiation
When an atom makes a transition from one stationary state of energy Ea to
another of energy Eb, it emits or absorbs a photon of light: Ea – Eb = hv
Bohr Model of Atom

Angular momentum quantized

nh
mvr = n=1,2,3,...
2p
(2p r = nl )

Energy expression
me e 4 1
En = - 2 2 . 2
8e0 h n

Spectral lines
me e 4 æ 1 1 ö
DE = 2 2 çç 2 - 2 ÷÷ = hn ni ,n f = 1,2,3,...
8e h è ni nf ø

Explains Rydberg formula

me e 4
R¥ = 2 2 =1.09678 x 10-2 nm-1
8e h
Ionization potential of H atom 13.6 eV
Photoelectric Effect: Wave –Particle Duality

Electromagnetic Radiation
E  E0 Sin(kx  t )

Wave energy is related to Intensity

I  E20 and is independent of 

Einstein borrowed Planck’s idea that ΔE=hν and

proposed that radiation itself existed as small packets
of energy (Quanta)now known as PHOTONS
1 2
EP  hv  KEM    mv  
2

 = Energy required to remove electron from surface

de Broglie Hypothesis: Mater waves
Since Nature likes symmetry,
Particles also should have wave-like nature

De Broglie wavelength
h h
 
p mv

Electron moving @ 106 m/s

h 6.6x10-34 J s
   7 1010 m
mv 9.1x10 Kg  1x10 m/s
-31 6

He-atom scattering
Diffraction pattern of He atoms at the speed
2347 m s-1 on a silicon nitride transmission
grating with 1000 lines per millimeter.
Calculated de Broglie wavelength 42.5x10-12 m
de Broglie wavelength too small for
macroscopic objects
Diffraction of Electrons : Wave –Particle Duality

Davisson-Germer Experiment

A beam of electrons is directed onto

the surface of a nickel crystal.
Electrons are scattered, and are
detected by means of a detector that
can be rotated through an angle θ.
When the Bragg condition
mλ = 2dsinθ was satisfied (d is the
distance between the nickel atom,
and m an integer) constructive
interference produces peaks of high
intensity
 Diffraction of Electrons : Wave –Particle Duality

G. P. Thomson Experiment

Electrons from an electron source

were accelerated towards a positive
electrode into which was drilled a
small hole. The resulting narrow
beam of electrons was directed
towards a thin film of nickel. The
lattice of nickel atoms acted as a
diffraction grating, producing a
typical diffraction pattern on a
screen
 Diffraction of Electrons : Wave –Particle Duality

The wavelength of the electrons was calculated, and found to be

in close agreement with that expected from the De Broglie
equation
Interference Pattern of Electrons : Wave –Particle Duality
Double Slit Experiment
Uncertainty Principle

Uncertainty principle
h
x.px 
4
Uncertainty Principle in ACTION!!!
Schrodinger’s philosophy

PARTICLES can be WAVES

and WAVES can be PARTICLES

• New theory is required to explain the behavior of electrons,

atoms and molecules

• Should be Probabilistic, not deterministic

• (non-Newtonian) in nature

• Wavelike equation for describing sub/atomic systems

 Schrodinger’s philosophy

PARTICLES can be WAVES

and WAVES can be PARTICLES

let me start with

classical wave equation
A concoction of
Schrodinger’s philosophy

Remember!
 Laws of Quantum Mechanics
The mathematical description of Quantum mechanics is built upon
the concept of an operator

Classical Variable QM Operator

Laws of Quantum Mechanics
The values which come up as result of an experiment are the
eigenvalues of the appropriate operator

In any measurement of observable associated with operator Â, the

only values that will be ever observed are the eigenvalues an, which
satisfy the eigenvalue equation:

Ψn are the eigenfunctions of the system and an are corresponding

eigenvalues

If the system is in state Ψk , a measurement on the system will yield

an eigenvalue ak