CH107

Physical Chemistry

Instructor for D2:

Rahul Maitra
 CH 107 Course Information
• Lectures: LA102
• Monday – 3:30-4:55 pm
• Thursday – 3:30-4:55 pm
• Contact:
• Tutorial and Discussion: • Email: rmaitra@chem.iitb.ac.in
• Wednesday – 4:00-4:55 pm
• Phone: 7185
• Office: Transit building (UG lab)
• Office Hour:
Room number 325
• Transit (UG Lab) building,
Room number 325
• Tuesday – 1:00-3:00 pm
• Wednesday – 1:00-3:00 pm
• Friday – 1:00-3:00 pm
 CH 107: Division 2
Tutorial venue and Teaching Assistants
Wednesday: 4:00 – 4:55 pm
D2/T1 LT-101 Poulomi Nandi

D2/T2 LT-102 Anish Chakraborty

D2/T3 LT-103 Prof. Arindam Chowdhury

D2/T4 LT-104 Ananya Sah

D2/T5 LT-105 Rahul Maitra

D2/T6 LT-106 Tejmani Behera

Attendance, marks change and course related issues:

Course Secretary: Ms. Charine Astrid

Central Facility, Chemistry Dept. 2nd floor
Email: charine@chem.iitb.ac.in
Phone: (022)2576 4159
CH 107 schedule and evaluation scheme

Duration 7 weeks  14 lectures of 1.5-hour

Quiz  MS Exam TBA
End-Semester Exam TBA

Evaluation Scheme
Quiz  Mid-Sem Exam ~18 Marks
End-Semester Exam ~24 Marks
Mini-quiz during tutorials ~8-9 Marks
Passing Marks 15 out of 50
As we explore Quantum Mechanics together……….
 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,
(often dealt with by engineers)

• Biotechnology and healthcare

• Energy Science – “Solar Energy” conversion
• Atmospheric Science - “Save the World”
• Nanoelectronics/Nanotechnology: Molecular Electronics
 Relevance of CH107?
CH-107

Apply QM principles to
predict the structure
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
 THE STORY SO FAR….
‘Unlike Newton’s mechanics, or Maxwell’s
electrodynamics, or Einstein’s relativity,
quantum theory was not created – or even
definitively packaged – by one individual,
and it retains to this day some of the scars of
its exhilarating but traumatic youth. There is
no general consensus as to what its
fundamental principles are, how it should be
taught, or what it really “means”.

Every competent physicist can “do”

quantum mechanics, but the stories we tell
ourselves about what we are doing are as
various as the tales of Scheherazade, and
almost implausible.

Richard Feynman (one of the greatest

practitioners) remarked, “I think I can safely
say that nobody understands quantum
mechanics” ‘
*Taken from an unidentified text book
 COURSE ELEMENTS

1. The fundamental laws of nature

➢ List the postulates of quantum mechanics

➢ Identify strategies to solve Schrodinger equation

2. Predict electronic energy levels and electronic

spectra in atoms

❑ Application of quantum mechanics to H-atom

to obtain quantization of energy and angular
momentum
❑ Predict how electrons are distributed around
nuclei
❑ Write an approximate wavefunction and
energy of multi-electron atoms
 COURSE ELEMENTS

3. Predict bonding between atoms from the

fundamental laws of nature

▪ Predict bonding using two approaches:

➢ Valence bond theory (VBT)
➢ Molecular orbital theory (MOT)
▪ Qualitatively compare the results of VBT and MOT in
context of predicting bonding

4. Predict molecular spectra

❑ Identify the general form of writing a spectra

for any arbitrary molecule
❑ Predict lineshapes of rotational, vibrational and
electronic spectra
❑ Using spectroscopy to compute bond length
and strengths
 Text books and resources

• Atkins Physical Chemistry – P.W. Atkins and R. Friedman

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
 COURSE ELEMENTS
1. The fundamental laws of nature

➢ List the postulates of quantum mechanics

➢ Identify strategies to solve Schrodinger equation

2. Predict electronic energy levels and electronic spectra

in atoms

3. Predict bonding between atoms from the fundamental

laws of nature

4. Predict molecular spectra

 THE QUANTUM MYSTERY

Electrons are Particles or Waves?

They are neither !!

But so is light !!!!

The mystery unfolds…….

 Double Slit Experiment: bullets

Reference: Feynman Lectures on Physics, volume 3.

Double Slit Experiment with waves

Reference: Feynman Lectures on Physics, volume 3.

 Double Slit Experiment: electrons

Reference: Feynman Lectures on Physics, volume 3.

Source: unidentified reference from internet

 Double Slit Experiment: Summary

Source: unidentified reference from internet

Wave? Particle? Matter wave? Wavicle?

Reference: Feynman Lectures on Physics, volume 3.

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
Watching the electrons from double slit experiment…

Pattern 1: Pattern 2:
Wave like Particle like
Uncertainty Principle

Uncertainty principle
h
x.px 
4
 Course Outcomes
Apply QM principles to
predict the structure
of atoms and molecules

1. The fundamental laws of nature

❑ List the postulates of quantum mechanics
❑ Identify strategies to solve Schrodinger equation
 Born Interpretation of Wavefunction
The state of a QM system is completely specified by Y(x,y,z,t) and all
possible information can be derived from Y
Y is a mathematical function; real or complex
Y*. Y dv is the probability that the particle lies in vol. dv, so Y*Y is the
probability density at that point

Normalization of Wave function: Probability of finding

a particle somewhere in the entire space has to be unity.

 Y ( x, y, z ).Y( x, y, z )dxdydz =  Y Yd = Y Y = 1

* *

all space all space

Dirac’s Bra-Ket notation

 Acceptable wavefunctions
Single Valued, continuous, differentiable, finite,
square integrable

Unacceptable because Unacceptable because

ψ is not single-valued ψ is not continuous
 Acceptable wavefunctions
Single Valued, continuous, differentiable, finite,
square integrable

Unacceptable because ψ is Unacceptable because

not differentiable ψ goes to infinity
 Acceptable wavefunctions
Single Valued, continuous, differentiable, finite,
square integrable

Unacceptable because ψ is
not square integrable

 dx|ψ( x)|  
2
−
Measurement Process: Schrodinger’s cat and wavefunction collapse
The Copenhagen Interpretation
Postulate-2:
The observables and operators…
The representation of operators…

Eigenfunctions and Eigenvalues…

The state of the system after measurement is assumed to “collapse” into an

eigenstate of the operator corresponding to the measurement. Repeated
measurements are likely to lead to different results.

Postulate-3:
The outcome of infinite number of measurements: the average value
(expectation value)

Described as the probability distribution of the measurement operator and may

or may not be continuous.
 Operators
I. Operators: Does “something” to whatever follows it
• Takes an Action: Simple operations - addition, multiplication
• Can be real or complex; Can be represented as matrices.
d 
1
−1
A f ( x) = g ( x) :  4, Cube, ,( ) , Sin, log, , ,   new function / number
dx y 0
Symmetry operators – rotation, reflection, inversion!
Operation →Changes/Perturbs function/system in some way!
→ act of measurement or perform an experiment

d
Linear Operators : A  c1 f1 ( x) + c2 f 2 ( x)  = c1 A f1 ( x) + c2 A f 2 ( x ); ex.
dx
but () −1 , SQR or 3 or Sin, Cos, exp, log : Nonlinear Operators

If A  g ( x) = h( x); B  f ( x)  = g ( x); AB  f ( x)  = A  B  f ( x)  = A  g ( x)  =31 h( x)

 
 Operator Formalism
To every observable in classical mechanics, there corresponds
a linear Hermitian operator (real or complex) in quantum mechanics
Classical quantity Quantum Mechanical operator

Position, x x̂
d
Momentum, px − i
dx

px2 2 d 2
Kinetic energy in 1-D, K x = −
2m 2m dx 2
Kinetic energy in 3-D,
2  2 2 2 
K=
1
( px2 + p y2 + pz2 ) −  2 + 2 + 2 
2m 2m  x y z 
(LAPLACIAN)

Potential Energy, V Multiply by V(x,y,z)

2  2 2 2 
Total Energy, E= K+V −  2 + 2 + 2 
2m  x y z 
+ V(x,y,z)

(HAMILTONAN OPERATOR)
 Real (observable) eigenvalues
In a measurement of a classical variable (associated with  satisfying the
ÂY = aY only real (not imaginary) eigenvalues (an) will ever be observed
There are many Eigen-fn(s) (or eigenstates) for the same QM
operator →like Sin and Cos are both eigenfunctions of op. D2

ÂY = aY
Yn → eigenfunctions or eigenstates or states
an →Eigenvalues (outcome of measurement)
As QM operators are Hermitian, if system is in state Yk, a
measurement on the system will yield a real eigenvalue ak
Only real eigenvalues will ever be observed, which will specify
a number corresponding to a classical variable for an eigenfunction

OPERATOR HAS TO BE HERIMITAN OERATOR → REAL EIGENVALUES

 IV. Average or Expectation value
So, prescription needed for average value of a classical observable

P( x) ~ Y dx = Y .Ydx (in 1D)

2 *

<a> corresponds to the mean value of a classical physical quantity

(observable), and A represents the corresponding QM operator

a =  Y * Aˆ Ydv = Y Aˆ Y
all space

 Y * Aˆ Ydv
Y Aˆ Y
a = all space
=

all space
Y * Ydv Y Y
 Time-Dependent Schrödinger Equation
 2
i Y ( x, t ) = −  x Y ( x, t ) + V ( x , t ) Y ( x , t )
2

t 2m
Very often, V(x,t) = V(x) → then special solutions to TDSE

Y( x, t ) =  ( x). f (t )
Product of space function and time function: separated out!
TIME − DEPENDENT PART of solution :
1 df (t ) df (t )  iE 
− =E  = −   dt
i f (t ) dt f (t )  

f (t ) ~ e−iEt /
 Time-Independent Schrödinger Equation
Y( x, t ) =  ( x). f (t )
Rearranging time − independent ( SPACE ) part :
2
1 d  ( x)
2
− + V ( x) = E
2m  ( x) dx 2

Time − Independent Schrodinger Equation :

H ( x) = E ( x) ; H  −
2 2
d
2
+ V ( x)
2m dx
For 1 particle (3D) system : solve TISE with 3 variables
 2
2
2 2 
−  2 + 2 + 2  ( x, y, z ) + V ( x, y, z ) ( x, y, z ) = E ( x, y, z )
2m  x y z 
 Stationary States
V ( x, t ) = V ( x ) Y( x, t ) =  ( x). f (t )
Y = f = ( f ) ( f )
2 2 *
Stationary states
(i.e. a solution) –
= (e iEt /
 *
)( e − iEt /
) Eigenstate of H
|Y|2 and Energy→
= e .  = 
2
Const. in time
0 *

 F (t )
Does not mean that the system is at rest (recap
Bohr’s stationary state). Probability/Energy does not
change with time when the V is time-independent 37
 Postulates of Quantum Mechanics
The state of a system is completely specified by a wave-
function Ψ(r,t). Square of “wavefunction” →probability density

To every observable in classical mechanics, there corresponds

a linear operator in quantum mechanics

In measurement of observable associated with operator A,

only values that will be observed are the eigenvalues of A

The average value of the observable corresponding to A is

a =  Y * Aˆ Yd
Ψ(x,y,z,t) of a system evolves as:

 2 2
i Y ( x, t ) = − Y ( x , t ) + V ( x , t ) Y ( x, t )
t 2m x 2