CH-111 2023:Physical

Chemistry
• Electronic Structure of Atoms
• Chemical Bonding

Instructor for D3 Batch

Dr. Achintya Kumar Dutta

Room 380, 2nd floor, Chemistry
Phone: x-7156
Whatsapp No. 9064136238

Email: achintya@chem.iitb.ac.in;
 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 CH111?
P Chem

Apply QM principles to
understand the behavior
of atoms and molecules

Physics O and I Chem

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 CH111:P is to understand: Why and
How…
 The bigger picture
Fundamentals of
PH-107 Quantum Physics 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 (18x1hr)
• Origin of Quantization ~3 lectures
Postulates of Quantum Mechanics
Particle in a Potential Well

•Electronic Structure in Atoms ~6 lectures

Hydrogen atom
Multi-electronic atoms

• Chemical Bonding ~6 lectures

Molecular Orbital Theory
Energetics/Electronic structure of homonuclear diatomics

• Molecular-Electronic Structure ~3 lectures

Heteronuclear diatomics and polyatomics, hybridization
Textbooks, Materials, and Resources
• Textbook: Physical Chemistry – I.N. Levine
• Textbook: Physical Chemistry – P.W. Atkins
• Reference Text: Physical Chemistry: A Molecular
Approach - McQuarrie and Simon

CH111 Course Material/lecture slides will be

uploaded in IITB Moodle every week
All important announcements in moodle and
WhatsApp group for D3 with all students &
AKD
Tutorial problems: Solve ahead of time (MQ!)
 Grading stuff
• Weekly mini-quiz (2 marks) – best 4 out of 5 (2x4=8)
During tutorials (similar to tut Qs)
No make-up or re-mini-quiz

•Quiz – 12 marks (~50 mins)

ASSISTANCE?
• Mid-Sem - 30 marks (~2 hrs) UG TAs in hostel!

Passing marks is typically 30% (<15 out of 50)

A+ grade is typically for >96% (>48 out of 50)

ATTENDANCE???
 Tutorial

Information about TAs:

T1: Achintya T2: Sudipta Chakraborty
T3: Ankit Kumar T4: Priya Bhandari

• They will be taking the Tutorial sessions

• Point of contact: For e.g. Language, any other issues etc.

What have you already knew
in a nutshell?
E  h
 h h
 
p mv

Davisson and Germer

George Thompson 11
 Wave-Particle Duality
Light can have “particle-like” and “wave-like”
properties; Matter (electrons & atoms) have
“particle-like” and “wave-like” properties
(we do not know what they really are!!)

Electrons (matter) or light

(“WAVICLE?”)
are both very weird, but
their behaviors are identical!!

When we refer to a (QM) particle,

What we really mean is a “wave-particle”
Exact position and momentum
iss “Indeterministic” or h
uncertain for
x.px 
submicroscopic
4
fast moving particles
Richard Feynman…
 Nature of submicroscopic atoms is not
understandable and beyond our perception

We deduce about their nature based on

indirect evidence, and then proceed to
describe it…
…in terms of quantities which we know from
our experience of the macroscopic world
(using analogy and contrast)

However, analogies may not always provide the

correct picture (if there is one!)
Richard Feynman on Quantum Behavior
They behave in their own inimitable yet
fascinating manner, which could be called
the “Quantum Mechanical way”

Inherently, “nature” at the atomic scale

is not deterministic, and their exact behaviors can
not be predicted – Probabilistic!
Best to be described mathematically!
 Need a new theory to understand
(dynamics of) electrons and atoms
• Probabilistic, not deterministic (non-newtonian)
• Wavelike equation for describing sub-atomic systems

   ( x, t )
i   ( x, t )  H
t
“Where did we get that (equation) from? Nowhere.
It is not possible to derive it from anything you
know.
It came out of the mind of Schrödinger.”
Schrodinger 1925!!! 17
Why believe in Schrodinger’s Eq.?
    2 2

i  ( x , t )     V  x , t   ( x , t )
t  2m x
2


Why did you believe in Newton’s

LAWs of motion?
Did you ever question their validity?

Laws  Based on Postulates or Axioms

Not been proven wrong experimentally
18
Erase your memory

19
 Postulates of Quantum Mechanics
The state of a system is completely specified by a wave-
function Ψ(r,t). Square of “wavefunction” probability density

Every observable in the classical world is related to a linear

Hermitian operator in quantum mechanics

Every measurement is associated with operator (A),

Values that will ever be observed are eigenvalues of A

The average value of the observable corresponding to A is

a    * Aˆ d
Any QM system evolves as (TDSE):
   2 2
i  ( x , t )    ( x, t )  V  x, t   ( x, t )
t 2m x 2
 What can you get from solving
the Schrodinger Equation?

Y is a mathematical function; real or complex

What is the meaning of ψ(x,t)?
A “wave” associated with matter?
 I. 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; Probability amplitude
Y*. Y dv is the probability that the particle lies in vol. dv,
so Y*Y is the probability density at that point

 can be complex :   f  ig and  *  f  ig

2 1882-1970
    ( f  ig )( f  ig )  f  g  
* 2 2

Normalization of Wave function: Probability of finding

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


all space
 * ( x, y, z ). ( x, y, z )dxdydz  
all space
* d     1

Dirac’s Bra-Ket notation

 Physically acceptable wavefunctions
1. Y must be normalizable
• Y is finite and Y 0 at boundaries/  
2. Y must be single-valued because y*y can not have two values!
3. Y is solution of 2º DE (Schrod. Eqn): Quadratically integrable
• y must be a continuous function in space
• slope of y i.e. dy/d(space) must also be continuous

Restrictions on wavefunction  Well-behaved wavefunctions

Single-point discontinuity sometimes acceptable “removable”

 Postulates of Quantum Mechanics
The state of a system is completely specified by a wave-
function Ψ(r,t). Square of “wavefunction” probability density

Every observable in the classical world is related to a linear

Hermitian operator in quantum mechanics

Every measurement is associated with operator (A),

Values that will ever be observed are eigenvalues of A

The average value of the observable corresponding to A is

a    * Aˆ d
Any QM system evolves as (TDSE):
   2 2
i  ( x , t )    ( x, t )  V  x, t   ( x, t )
t 2m x 2
 Mathematical Tools-1: 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.
1
 1 d 
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 )   h( x )
  25
 II. 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  + V(x,y,z)
2m  x y z 
(HAMILTONAN OPERATOR)
 TDSE: 2nd order partial differential equation
In 1 spatial dimension,  ( x, t ), Schrodinger Equation
 2  2
    ( x, t )  ( x, t )
i   ( x, t )    ( x , t )  V
t 2m x 2

   2  2 
i   ( x, t )     V ( x, t )   ( x, t )
t  2 m x 2

Hamiltonian (Total Energy  KE  PE ) Operator
   2
2
 x  V ( x, t ) where,  2
x   2
H  in 1D
2m x 2

   ( x, t )
i   ( x, t )  H
t
 Postulates of Quantum Mechanics
The state of a system is completely specified by a wave-
function Ψ(r,t). Square of “wavefunction” probability density

Every observable in the classical world is related to a linear

Hermitian operator in quantum mechanics

Every measurement is associated with operator (A),

Values that will ever be observed are eigenvalues of A

The average value of the observable corresponding to A is

a    * Aˆ d
Any QM system evolves as (TDSE):
   2 2
i  ( x , t )    ( x, t )  V  x, t   ( x, t )
t 2m x 2
 Math-2. Eigenfunction/Eigenvalue equations
Operator operating on a function re-generates the same function
(which is called eigenfunction) multiplied by a number (eigenvalue)

Given A, find  ( x ), so that A

 ( x)  a ( x); a  (#) : Eigenvalue Equation

n
n
A  D d d 
n
; If   Sin( x ); D
dx dx
Can  ( x) be e x or Sin x ?     Cos ( x )
D
If so, Eigenvalues, a  ?  2    2 Sin( x )   2
D

 d n x
D  ( x)  n e   n ( x)  Yes ! EV :  n
n

dx
 n Sin x  (#)  Sin x for n  even, YES! Eigenfunction
D

 n Sin x (#)  Sin x for n  odd , NOT Eigenfucntion
D
 III. Real (observable) eigenvalues
In measurement of a classical variable (operator  satisfying Â  a )
only real (not imaginary) eigenvalues (an) will ever be observed

There are many Eigen-f(n)s (or eigenstates) for the same QM

operator like Sin and Cos are both eigenfunctions of op. D2

ˆA n  an  n Aˆ     Aˆ a   a    a
1 1 2 2 1 or a2
Yn  eigenfunctions or eigenstates or states
an Eigenvalues (outcomes of measurements)
A measurement on system cannot yield an imaginary eigenvalue
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

 Math-3. Probability Distributions: Expectation
(Average/Mean value) and Most-Probable Value
3
 M  2  Mv2
f (v)  4  
2
ve 2 RT

 2 RT 

If P(x) is the probability distribution

dP ( x)
Most Probable (Modal) value at Maxima  0
dx
n n
Mean : E ( x)  x   x j Pj ( x j ) and E ( x 2 )  x 2   x 2j Pj ( x j )
j 1 j 1
 Postulates of Quantum Mechanics
The state of a system is completely specified by a wave-
function Ψ(r,t). Square of “wavefunction” probability density

Every observable in the classical world is related to a linear

Hermitian operator in quantum mechanics

Every measurement is associated with operator (A),

Values that will ever be observed are eigenvalues of A

The average value of the observable corresponding to A is

a    * Aˆ d
Any QM system evolves as (TDSE):
   2 2
i  ( x , t )    ( x, t )  V  x, t   ( x, t )
t 2m x 2
 IV. Average or Expectation value
So, prescription needed for average value of a classical observable
2
P ( x) ~  dx   .dx (in 1D) *

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

(observable), and A represents the corresponding QM operator
 
A.P ( x)dx = A.  2 dx ~  * Aˆ dx
In 1D a  

 

all space

a    * Aˆ dv   Aˆ 
all space

  * Aˆ dv
all space  Aˆ 
a  

all space
 * dv  
 Before and after measurement

Measurement: Property has a value of P

Before measurement:

Realist: Value = P (Einstein)

Quantum theory is incomplete

Orthodox: Entanglement (Bohr,

Copenhagen interpretation)
Measurement produces the value

Agnostic: Don’t know, don’t care

 Before and after measurement

Measurement: Property has a value of P

Before measurement: Immediately after measurement:

Realist: Value = P (Einstein) Same Value = P

Quantum theory is incomplete

Orthodox: Entanglement (Bohr,

Copenhagen interpretation)
Measurement produces the value

Agnostic: Don’t know, don’t care

Wavefunction collapse
 Postulates of Quantum Mechanics
The state of a system is completely specified by a wave-
function Ψ(r,t). Square of “wavefunction” probability density

Every observable in the classical world is related to a linear

Hermitian operator in quantum mechanics

Every measurement is associated with operator (A),

Values that will ever be observed are eigenvalues of A

The average value of the observable corresponding to A is

a    * Aˆ d
Any QM system evolves as (TDSE):
   2 2
i  ( x , t )    ( x, t )  V  x, t   ( x, t )
t 2m x 2
Math-4: 2nd order Partial Differential Equations
2nd order Normal Differential Equation (DE) d 2 f ( x)
With one variable (Simple Harmonic Motion) 2
 kf ( x)  C
dx
Partial Differential Equation (PDE) contains two or more variables
 2 F ( x, y)  2 F ( x, y ) F ( x, y ) F ( x, y )
    kF ( x, y )  0
x 2
y 2
x y
To Solve any PDE  Separation of Variables (or else, can not solve)
d 2 f ( x ) df ( x ) d 2 f ( y ) df ( y )
2
  mf ( x )  2
  nf ( y )
dx dx dy dy
LHS ( x)  RHS ( y )  F1 ( x)  F2 ( y )  const.
d 2 f ( x ) df ( x )
2
  mf ( x)  const.(say k)
dx dx Two normal DEs
d 2 f ( y ) df ( y ) with single variable
 2
  nf ( y )  k ( same const.)
dy dy
 Time-Dependent Schrödinger Equation
  2
i  ( x , t )    x  ( x , t )  V ( x , t )  ( x, t )
2

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

 ( 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 / 
 Separation of variables

[ ]
2
𝜕 ℏ 2
𝑖 ℏ 𝜓𝑛 (𝑥 , 𝑦 , 𝑧)𝜙 (𝑡)= − ∇ +𝑉 (𝑥 , 𝑦 , 𝑧) 𝜓 𝑛 (𝑥 , 𝑦 , 𝑧) 𝜙(𝑡)
𝜕𝑡 2𝑚

𝜕 𝜙 (𝑡)
[ ]
2
ℏ 2
𝜓 𝑛 ( 𝑥 , 𝑦 , 𝑧 ) .𝑖 ℏ =𝜙(𝑡 ) − ∇ 𝜓 𝑛 ( 𝑥 , 𝑦 , 𝑧 ) +𝑉 ( 𝑥 , 𝑦 , 𝑧 ) .𝜓 𝑛 ( 𝑥 , 𝑦 , 𝑧 )
𝜕𝑡 2𝑚
𝑖 ℏ 𝜕 𝜙 (𝑡)
[ ] ¿𝑊
2
ℏ 2
=− ∇ 𝜓𝑛 ( 𝑥 , 𝑦 , 𝑧 )+𝑉 ( 𝑥 , 𝑦 , 𝑧 ) . 𝜓𝑛 ( 𝑥 , 𝑦 , 𝑧 )
𝜙 (𝑡) 𝜕 𝑡 2 𝑚. 𝜓 𝑛 ( 𝑥 , 𝑦 , 𝑧 )
Separation constant
Ψ 𝑛 ( 𝑥 , 𝑦 , 𝑧 , 𝑡 )=𝜓 𝑛 (𝑥 , 𝑦 , 𝑧)𝜙 (𝑡)
 Separation of variables

[ ]
2
𝜕 ℏ 2
𝑖 ℏ 𝜓𝑛 (𝑥 , 𝑦 , 𝑧)𝜙 (𝑡)= − ∇ +𝑉 (𝑥 , 𝑦 , 𝑧) 𝜓 𝑛 (𝑥 , 𝑦 , 𝑧) 𝜙(𝑡)
𝜕𝑡 2𝑚 ^
𝐻,Hamiltonian
operator
𝜕 𝜙 (𝑡)
[ ]
2
ℏ 2
𝜓 𝑛 ( 𝑥 , 𝑦 , 𝑧 ) .𝑖 ℏ =𝜙(𝑡 ) − ∇ 𝜓 𝑛 ( 𝑥 , 𝑦 , 𝑧 ) +𝑉 ( 𝑥 , 𝑦 , 𝑧 ) .𝜓 𝑛 ( 𝑥 , 𝑦 , 𝑧 )
𝜕𝑡 2𝑚
𝑖 ℏ 𝜕 𝜙 (𝑡)
[ ] ¿𝑊
2
ℏ 2
=− ∇ 𝜓𝑛 ( 𝑥 , 𝑦 , 𝑧 )+𝑉 ( 𝑥 , 𝑦 , 𝑧 ) . 𝜓𝑛 ( 𝑥 , 𝑦 , 𝑧 )
𝜙 (𝑡) 𝜕 𝑡 2 𝑚. 𝜓 𝑛 ( 𝑥 , 𝑦 , 𝑧 )

𝑖 ℏ 𝜕 𝜙 (𝑡)
𝜙 (𝑡) 𝜕 𝑡
=𝑊 −
;
[ ℏ2
2𝑚 . 𝜓 𝑛 ( 𝑥 , 𝑦 , 𝑧 ) ]
∇2 𝜓𝑛 ( 𝑥 , 𝑦 , 𝑧 )+ 𝑉 ( 𝑥 , 𝑦 , 𝑧 ) . 𝜓𝑛 ( 𝑥 , 𝑦 , 𝑧 ) =𝑊

−𝑖𝑊𝑡 / ℏ
𝑒 Ψ 𝑛 ( 𝑥 , 𝑦 , 𝑧 , 𝑡 )=𝜓 𝑛 (𝑥 , 𝑦 , 𝑧)𝑒
− 𝑖𝑊𝑡 / ℏ
 Time-Independent Schrödinger Equation
 ( 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 :

2 2
 d
H ( x)  E ( x) ; H  
 
2
 V ( x)
2m dx
For 1 particle (3D ) system : 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 
Schrödinger being inducted as an angel…
 Free Particle

Time-independent Schrodinger equation

For a free particle V(x)=0

There are no external forces acting
 Free Particle
m
x

Second-order linear differential equation

Let us assume
 ( x )  A sin kx  B cos kx
Trial Solution
 Free Particle
m
x

Second-order linear differential equation

Let us assume
 ( x )  A sin kx  B cos kx
Trial Solution
Free Particle
m
x
 Free Particle
m
x
de Broglie wave
2 2 2 k 2 2mE
k  ( x )  E  ( x )  E  k
2m 2m 

There are no restrictions on k

E can have any value
Energies of free particles are
continuous

No Quantization All energies are allowed

 Free Particle
m
x
de Broglie wave
2 2 2 k 2 2mE
k  ( x )  E  ( x )  E  k
2m 2m 

There are no restrictions on k

E can have any value
Energies of free particles are
continuous

No Quantization All energies are allowed

Is this a good wavefunction?
 Particle in 1-D Box

For x < 0 and x > L  V = ∞ For 0 ≤ x ≤ L  V = 0

Zero

Trial Solution:

Energy:
Wavefunction should be continuous:
Boundary condition
 Particle in 1-D Box

n = 1, 2, 3, 4, …..

n ≠ 0, as wavefunction cannot be zero everywhere

For x < 0 and x > L  V = ∞ For 0 ≤ x ≤ L  V = 0

Trial Solution:

Energy:
Boundary condition
 Particle in 1-D Box: Normalization

n = 1, 2, 3, 4, …..

n ≠ 0, as wavefunction cannot be zero everywhere

[ 𝐿
]
𝐿

( )
𝐿 𝐿
1 1
2
= ∫ 1 −2 𝑐𝑜𝑠
𝐴 2 0
2𝑛 𝜋
𝐿
1
(
𝑥¿ 𝑑𝑥 ∫ 𝑑𝑥 −∫ 𝑐𝑜𝑠
2 0 0
2𝑛 𝜋
𝐿
¿
𝑥 𝑑𝑥 2 − 0 )
Particle in 1-D Box: Wavefunctiona

𝜓 ( 𝑥 )=
√ 2 𝑛𝜋𝑥
𝐿
sin
𝐿
n = 1, 2, 3, 4, …..

n ≠ 0, as wavefunction cannot be zero everywhere

Orthogonality

.
𝐿
1
¿
𝐿
∫ ¿ ¿
0

¿0

Is the first derivative continuous?

Not at x = 0 and x = L
Particle in 1-D Box: Energy

𝜓 ( 𝑥 )=
√ 2 𝑛𝜋𝑥
𝐿
sin
𝐿
n = 1, 2, 3, 4, …..

n ≠ 0, as wavefunction cannot be zero everywhere

• Energy is quantized!

Boundary conditions are the origin of quantization

• Energy separation increases with increasing values of n

h2
• Lowest possible energy is non-zero: Zero point energy𝐸 1 =
8 𝑚 𝐿2

• Larger the box, smaller the energy of hν

 Particle in 1-D Box: Spectroscopy

n=1,3.. Symmetric wrt inversion (even function)

Wavefunction: n=2,4.. Anti-Symmetric (odd function)

Number of Nodes (zero crossings) = n-1

Transition is allowed when

Transition Moment Integral ⟨ 𝜓 2| 𝑥|𝜓 1 ⟩ ≠ 0
𝜇=𝑒 . 𝑥
Non-zero integral: Symmetric integrand Antisymmetric

If one wave function is symmetric, then the other should be antisymmetric

Selection rule:

Odd to even, even to odd transitions are allowed

 Particle in 1-D Box: Examples in Chemistry

Hexatriene: a linear molecule of length 7.3 Å

It absorbs at 258 nm
Use particle in a box model to explain the results.
𝜓 ( 𝑥 )=
√ 2 𝑛𝜋𝑥
𝐿
sin
𝐿
n = 1, 2, 3, 4, …..



 Compare with the experimental value of 258 nm
Particle in a box is a good first approximation
Six  electrons fill
lower three levels
 Particle in 1-D Box: Examples in Chemistry

√
Electronic spectra of conjugated molecules 2 𝑛𝜋𝑥 n = 1, 2, 3, 4, …..
𝜓 ( 𝑥 )= sin
𝐿 𝐿

Increase in bridge length increase the

emission wavelength.

Predicts correct trend and gets the

wavelength almost right.

Particle in a box is a good first

approximation

Β-carotene is orange because of 11

conjugated double bonds
 Particle in 1-D Box: Examples in Chemistry

Quantum Dots – Quasi-particle (exciton) in a Box! 𝜓 ( 𝑥 )=

√ 2 𝑛𝜋𝑥
𝐿
sin
𝐿
n = 1, 2, 3, 4, …..

CB
CB
CB

VB
VB
VB
 Applications of Q-Dots/–Rods/-Wells
range from biology to solar photovoltaics
to LED based displays

Quantum-Dot based Quantum-Dot based in-vivo

Solar Cells imaging for tumor/cancer
58
Expectation value: Position
 Expectation value: Position

Probability in a thin strip for different n and x values

 Particle in a 2-D box
Separation of variables

V=0

Ly

Lx

Square Box
 Lx = Ly = L
Expectation value: Momentum

Eigenfunctions:
Equal magnitude,
opposite direction

√ [ ]
𝑖𝑛 𝜋 𝑥 −𝑖𝑛 𝜋 𝑥
2 1 𝐿 𝐿
𝜓 𝑛= . 𝑒 −𝑒
𝐿 𝑖

Equal probability for propagation

in the two directions
Degeneracy is manifestation of symmetry

Energy

Recap: Crystal Field splitting

63
 Particle in a 2-D box: Wavefuntiona

Number of nodes = nx+ny-2

 Rectangular box

V=0
Ly

Lx

(1, 2) and (2, 1) levels, for example,

have same energy in square box, but not in rectangular box

Symmetry and degeneracy go hand in hand

3D box
 Particle in a box: Take home messages

• Schrodinger equation is exactly solvable

• Boundary conditions: Quantization

• More nodes in wavefunction, higher is the associated energy

• Eigenfunction of linear momentum operator

• Simple model, finds application in Chemistry

• Increase in dimensionality: Separation of variable

• Symmetry and degeneracy go hand in hand

• Beyond 3D functions

• Testing ground for more sophisticated treatment

What happens if the potential barrier is finite?