PYL101: EM Waves & Quantum Mechanics

Quantum Mechanics - Lecture 5

Brajesh Kumar Mani

(bkmani@physics.iitd.ac.in)

• Schedule: Monday & Thursday (8:00 – 9:30,

Slot A)
• TAs: Reference Books
Radhika T P (phz198033@physics.iitd.ac.in )
Manoj Singh (phz198494@physics.iitd.ac.in )

• Tutorials: From January 25th, Monday-Friday,

03:00PM-04:00PM
 I will cover the following topics:
Module 8: Quantum Mechanical Operators: observables and operators,
linear operators, eigenvalues and eigen vectors of operators,
Hermitian operators, product of operators, expectation values
and uncertainty relations,

Module 9: Time-Independent Schrodinger Equation: stationary states, free

particle solution, bound states
 I will cover the following topics:
Module 8: Quantum Mechanical Operators: observables and operators,
linear operators, eigenvalues and eigen vectors of operators,
Hermitian operators, product of operators, expectation values
and uncertainty relations,

Module 9: Time-Independent Schrodinger Equation: stationary states, free

particle solution, bound states

Module 10: One Dimensional Problems: 1-D infinite potential well, 1-D finite
potential well, and quantum mechanical tunneling and alpha-decay.

(will be covered by Prof. Saswata Bhattacharya)

 A quick revision of what you have done so far
Birth of Quantum Mechanics
The “Classical Physics” fails miserably to explain

o the dynamics of the particles moving with very high speeds (comparable to the speed of
light)
o the structure and dynamics of particles/systems at microscopic level. For example, the
structure of atoms and molecules, and interaction with light.

1. The Particle-like 2. The Wave-like Behaviour 3. The Puzzling Stability

Behaviour of Waves of Particles of the Atom
• de Broglie hypothesis (1923) • What is the origin of
• Black-body radiation (1900)
• Electron diffraction (Davisson- atomic spectra?
• Photoelectric effect (1905)
Germer experiment) (1927)
• Compton effect (1923)
• Wave particle duali
 A quick revision of what you have done so far
Birth of Quantum Mechanics
The “Classical Physics” fails miserably to explain

o the dynamics of the particles moving with very high speeds (comparable to the speed of
light)
o the structure and dynamics of particles/systems at microscopic level. For example, the
structure of atoms and molecules, and interaction with light.

1. The Particle-like 2. The Wave-like Behaviour 3. The Puzzling Stability

Behaviour of Waves of Particles of the Atom
• de Broglie hypothesis (1923) • What is the origin of
• Black-body radiation (1900)
• Electron diffraction (Davisson- atomic spectra?
• Photoelectric effect (1905)
Germer experiment) (1927)
• Compton effect (1923)

Wave-Particle Duality: Complementarity

 A quick revision of what you have done so far
Wave Function in Quantum Mechanics

Classical Mechanics:
We can determine all these properties by
solving the Newton’s equation with appropriate Given: mass, force acting on the mass
boundary conditions.
𝑑2 𝑥 Wants to know: position, velocity, momentum
𝑚 2 = 𝐹 𝑥, 𝑡
𝑑𝑡 and kinetic energy at certain time t

Quantum Mechanics: “a microscopic particle”

In principle, we can determine all these properties if we know the wave function
Ψ 𝑥, 𝑡 of the particle. And, the wave function can be obtained by solving the equation

𝜕Ψ 𝑥,𝑡 ℏ2 𝜕2 Ψ 𝑥,𝑡 BC: at t = 0, what is Ψ 𝑥, 0 ?

𝑖ℏ = − + 𝑉 𝑥, 𝑡 Ψ x, t
𝜕𝑡 2𝑚 𝜕𝑡 2

time dependent Schrodinger equation

 A quick revision of what you have done so far
o Ψ is a continuous function.
o It represents the amplitude of the matter wave associates with particle.
o It contains the information about the probability that one would measure, but cannot give
pre-determined results.
𝑏
න Ψ 𝑥, 𝑡 2 𝑑𝑥 = Probability of finding the particle between 𝑎 and 𝑏 at time 𝑡
𝑎
where, Ψ 𝑥, 𝑡 2 = Ψ ∗ 𝑥, 𝑡 Ψ 𝑥, 𝑡 , and Ψ 𝑥, 𝑡 represents the
probability amplitude. Statistical Interpretation (Born, 1926)

• A wave function describing a particle at position x and time t can be represented by

Ψ 𝑥, 𝑡 𝑂𝑟 < 𝑥, 𝑡|Ψ > 𝑜𝑟 |Ψ >

(Ordinary representation) (Dirac representation)

• For every ket vector there is a corresponding dual vector, called the “bra” vector, which belongs a
dual vector space. That is,
|Ψ > x1 x2
< Ψ| (one-to-one correspondence )
New story begins
from here . . . . . . . .
 Operators in Quantum Mechanics
o An operator is a mathematical object that maps one quantum mechanical wave function to other.

𝐴መ Ψ 𝑥, 𝑡 = Φ 𝑥, 𝑡

old wave function new wave function

 Operators in Quantum Mechanics
o An operator is a mathematical object that maps one quantum mechanical wave function to other.

𝐴መ Ψ 𝑥, 𝑡 = Φ 𝑥, 𝑡

old wave function new wave function

o For each observable (position, linear momentum, angular momentum, energy, etc.) in quantum
mechanics, there is a corresponding operator.
 Operators in Quantum Mechanics
o An operator is a mathematical object that maps one quantum mechanical wave function to other.

𝐴መ Ψ 𝑥, 𝑡 = Φ 𝑥, 𝑡

old wave function new wave function

o For each observable (position, linear momentum, angular momentum, energy, etc.) in quantum
mechanics, there is a corresponding operator.

o If we can write Φ in terms Ψ such that Φ 𝑥, 𝑡 = 𝑎 Ψ 𝑥, 𝑡 then

𝐴መ Ψ 𝑥, 𝑡 = 𝑎 Ψ 𝑥, 𝑡 , (the eigenvalue equation) Eq.(1)

෡ and 𝑎 a real number for physical systems is the

Ψ 𝑥, 𝑡 is called an eigenfunction of A
corresponding eigenvalue.
 Operators in Quantum Mechanics
o If we cannot write Φ in terms of Ψ, Φ 𝑥, 𝑡 = 𝑎 Ψ ′ 𝑥, 𝑡 then

𝐴መ Ψ 𝑥, 𝑡 = 𝑎 Ψ ′ 𝑥, 𝑡 , (Not an eigenvalue equation)

෡.
Ψ 𝑥, 𝑡 is NOT an eigenfunction of A
 Operators in Quantum Mechanics
o If we cannot write Φ in terms of Ψ, Φ 𝑥, 𝑡 = 𝑎 Ψ ′ 𝑥, 𝑡 then

𝐴መ Ψ 𝑥, 𝑡 = 𝑎 Ψ ′ 𝑥, 𝑡 , (Not an eigenvalue equation)

෡.
Ψ 𝑥, 𝑡 is NOT an eigenfunction of A

Physical interpretation of eigenvalue equation:

Case I: Consider that the particle is in the state Ψ 𝑥, 𝑡 :

Using the eigenvalue equation, we can write

∞ ∞ ∞
‫׬‬−∞ Ψ ∗ 𝑥, 𝑡 𝐴መ Ψ 𝑥, 𝑡 𝑑𝑥 = ‫׬‬−∞ Ψ ∗ 𝑥, 𝑡 𝑎 Ψ 𝑥, 𝑡 𝑑𝑥 = 𝑎 ‫׬‬−∞ Ψ ∗ 𝑥, 𝑡 Ψ 𝑥, 𝑡 𝑑𝑥 = 𝑎

“if you do a measurement of the observable A, and if the particle in state Ψ then measured value
will be the eigenvalue of the operator A ෡"
 Operators in Quantum Mechanics
o If we cannot write Φ in terms of Ψ, Φ 𝑥, 𝑡 = 𝑎 Ψ ′ 𝑥, 𝑡 then

𝐴መ Ψ 𝑥, 𝑡 = 𝑎 Ψ ′ 𝑥, 𝑡 , (Not an eigenvalue equation)

෡.
Ψ 𝑥, 𝑡 is NOT an eigenfunction of A

Physical interpretation of eigenvalue equation:

Case I: Consider that the particle is in the state Ψ 𝑥, 𝑡 :

Using the eigenvalue equation, we can write

∞ ∞ ∞
‫׬‬−∞ Ψ ∗ 𝑥, 𝑡 𝐴መ Ψ 𝑥, 𝑡 𝑑𝑥 = ‫׬‬−∞ Ψ ∗ 𝑥, 𝑡 𝑎 Ψ 𝑥, 𝑡 𝑑𝑥 = 𝑎 ‫׬‬−∞ Ψ ∗ 𝑥, 𝑡 Ψ 𝑥, 𝑡 𝑑𝑥 = 𝑎

“if you do a measurement of the observable A, and if the particle in state Ψ then measured value
will be the eigenvalue of the operator A ෡"
The expectation value of the observable A in the state Ψ 𝑥, 𝑡 . It can be denoted as
መ
<A>Ψ or <A> or < Ψ|𝐴|Ψ>.
 Operators in Quantum Mechanics
“The expectation value of an observable is the average of repeated measurements on an ensemble of
identically prepared systems”

“It is NOT the average of the repeated measurements on the same system”
 Operators in Quantum Mechanics
“The expectation value of an observable is the average of repeated measurements on an ensemble of
identically prepared systems”

“It is NOT the average of the repeated measurements on the same system”

Case II: Consider that the particle is in any general state Φ 𝑥, 𝑡 :

Using the eigenvalue equation, we can write

∞ ∞ ∞
‫׬‬−∞ Φ∗ 𝑥, 𝑡 𝐴መ Ψ 𝑥, 𝑡 𝑑𝑥 = ‫׬‬−∞ Φ∗ 𝑥, 𝑡 𝑎 Ψ 𝑥, 𝑡 𝑑𝑥 = 𝑎 ‫׬‬−∞ Φ∗ 𝑥, 𝑡 Ψ 𝑥, 𝑡 𝑑𝑥

 if the particle is in the general state Φ then the measured value will be “a” with probability |Φ∗ Ψ|2 .
 Operators in Quantum Mechanics
“The expectation value of an observable is the average of repeated measurements on an ensemble of
identically prepared systems”

“It is NOT the average of the repeated measurements on the same system”

Case II: Consider that the particle is in any general state Φ 𝑥, 𝑡 :

Using the eigenvalue equation, we can write

∞ ∞ ∞
‫׬‬−∞ Φ∗ 𝑥, 𝑡 𝐴መ Ψ 𝑥, 𝑡 𝑑𝑥 = ‫׬‬−∞ Φ∗ 𝑥, 𝑡 𝑎 Ψ 𝑥, 𝑡 𝑑𝑥 = 𝑎 ‫׬‬−∞ Φ∗ 𝑥, 𝑡 Ψ 𝑥, 𝑡 𝑑𝑥

 if the particle is in the general state Φ then the measured value will be “a” with probability |Φ∗ Ψ|2 .

the matrix element of the observable A with respect to states Φ and Ψ.

መ
We denote it as < Φ |𝐴|Ψ>
 Operators in Quantum Mechanics
Example of Operators
Physical quantity Operator Operation
Position 𝑟Ԧ 𝑟Ƹ 𝑟 Ψ 𝑟, 𝑡

ℏ ℏ
Linear momentum 𝑝Ԧ 𝛻 𝛻Ψ 𝑟, 𝑡
𝑖 𝑖

ℏ ℏ
Angular momentum 𝐿 𝑟Ԧ × 𝛻 (𝑟 × 𝛻)Ψ 𝑟, 𝑡
𝑖 𝑖

ℏ2 2 ℏ2 2
Kinetic energy (T) − 𝛻 − 𝛻 Ψ 𝑟, 𝑡
2𝑚 2𝑚

Potential energy (V) 𝑉 𝑟Ԧ 𝑉 𝑟Ԧ Ψ 𝑟, 𝑡

ℏ2 2 ℏ2 2
Total energy (E) − 𝛻 + 𝑉 𝑟Ԧ − 𝛻 Ψ 𝑟, 𝑡 + 𝑉 𝑟Ԧ Ψ 𝑟, 𝑡
2𝑚 2𝑚

… we will do more on this later….

 Operators in Quantum Mechanics
Linear Operators
An operator 𝐴መ is said to be linear if it obeys the distributive law. That is, for wave functions Ψ1 and Ψ2 ,
and complex numbers 𝛼 and 𝛽, it satisfies the relation

𝐴መ 𝛼Ψ1 + 𝛽Ψ2 = 𝛼 𝐴መ Ψ1 + 𝛽 𝐴መ Ψ2

“most operators in quantum mechanics are linear operator”

 Operators in Quantum Mechanics
Linear Operators
An operator 𝐴መ is said to be linear if it obeys the distributive law. That is, for wave functions Ψ1 and Ψ2 ,
and complex numbers 𝛼 and 𝛽, it satisfies the relation

𝐴መ 𝛼Ψ1 + 𝛽Ψ2 = 𝛼 𝐴መ Ψ1 + 𝛽 𝐴መ Ψ2

“most operators in quantum mechanics are linear operator”

Hermitian Operators
An operator 𝐴መ is said to be Hermitian if for any two wave functions Ψ1 and Ψ2 , it satisfies the relation
∞ ∞
∗
න Ψ1∗ 𝐴መ Ψ2 𝑑𝑥 = න 𝐴Ψ1 Ψ2 𝑑𝑥
−∞ −∞
OR
An operator 𝐴መ is said to be Hermitian if it is equal to its adjoint 𝐴† . That is

𝐴መ = 𝐴መ † ⇒ < Ψ1 𝐴 Ψ2 > =< Ψ2 𝐴 Ψ1 >∗

 Operators in Quantum Mechanics
“ any operator corresponding to a physical observable is a Hermition operator”

“ all quantum mechanical operators which represent physical observables are Hermitian”

Important Properties of Hermitian operators:

• The eigenvalues of the Hermitian operators are real.

Homework problem 1
• The eigenvectors corresponding to two different eigenvalues of
a Hermitian operator are orthogonal to each other.
 Operators in Quantum Mechanics
Projection operator
If |Ψ > is a normalized wave function, then the projection operator is defined as

෡ = |Ψ >< Ψ|
P (ket-bra) (also called the outer product)
 Operators in Quantum Mechanics
Projection operator
If |Ψ > is a normalized wave function, then the projection operator is defined as

෡ = |Ψ >< Ψ|
P (ket-bra) (also called the outer product)

෡ acting on a different state |Φ >

• Lets consider P

෡ Φ>=
P Ψ >< Ψ Φ > = |Ψ > < Ψ Φ > = < Ψ Φ > |Ψ >

2
 it projects the state |Φ > onto the state |Ψ > with probability < Ψ|Φ >

• It is Hermitian: ෡† = P
P ෡
Homework problem 2
• It is idempotent ෡2
P ෡
=P
 Operators in Quantum Mechanics
Product of operators
The product of two operators generally do not obey the commutative relation. That is
𝐴መ 𝐵෠ ≠ 𝐵෠ 𝐴መ

 “the order of the application is important”. The operators 𝐴መ and 𝐵෠ are

called the non − commutating operators.

From above relation we can write: 𝐴መ 𝐵෠ − 𝐵෠ 𝐴መ ≠ 0 ⇒ 𝐴,

መ 𝐵෠ ≠ 0

“commutator operator”
 Operators in Quantum Mechanics
Product of operators
The product of two operators generally do not obey the commutative relation. That is
𝐴መ 𝐵෠ ≠ 𝐵෠ 𝐴መ

 “the order of the application is important”. The operators 𝐴መ and 𝐵෠ are

called the non − commutating operators.

From above relation we can write: 𝐴መ 𝐵෠ − 𝐵෠ 𝐴መ ≠ 0 ⇒ 𝐴,

መ 𝐵෠ ≠ 0

“commutator operator”
Example: Position and momentum operators are non-commutating operators as
𝑥,
ො 𝑝Ƹ𝑥 = 𝑥ො 𝑝ෝ 𝑥 − 𝑝Ƹ𝑥 𝑥ො = 𝑖ℏ
 Operators in Quantum Mechanics
Product of operators
The product of two operators generally do not obey the commutative relation. That is
𝐴መ 𝐵෠ ≠ 𝐵෠ 𝐴መ

 “the order of the application is important”. The operators 𝐴መ and 𝐵෠ are

called the non − commutating operators.

From above relation we can write: 𝐴መ 𝐵෠ − 𝐵෠ 𝐴መ ≠ 0 ⇒ 𝐴,

መ 𝐵෠ ≠ 0

“commutator operator”
Example: Position and momentum operators are non-commutating operators as
𝑥,
ො 𝑝Ƹ𝑥 = 𝑥ො 𝑝ෝ 𝑥 − 𝑝Ƹ𝑥 𝑥ො = 𝑖ℏ
• If 𝐴መ 𝐵෠ = 𝐵෠ 𝐴መ ⇒ 𝐴,
መ 𝐵෠ = 0, then A
෡ and B
෡ are called the "commutating operators".

 "𝐴መ and B
෡ can have the same eigen functions".

Example: 𝑥,
ො 𝑝Ƹ𝑦 = 𝑥ො 𝑝ෝ 𝑦 − 𝑝Ƹ𝑦 𝑥ො = 0
 Operators in Quantum Mechanics
Example Problem 1:
 Operators in Quantum Mechanics
Example Problem 1:

<𝜓 𝐴 𝜓>
Solution: If 𝜓 is not normalized, the expectation value is < 𝐴መ > =
<𝜓|𝜓>
 Operators in Quantum Mechanics
Example Problem 1:

<𝜓 𝐴 𝜓>
Solution: If 𝜓 is not normalized, the expectation value is < 𝐴መ > =
<𝜓|𝜓>
Operators in Quantum Mechanics
 Operators in Quantum Mechanics

Example Problem 2: Prove the commutation relations (a) 𝑥,

ො 𝑝Ƹ𝑥 = 𝑖ℏ b 𝑥,
ො 𝑝Ƹ𝑦 = 0
Solution: (a) Let us assume 𝜓 𝑥 represent the wave function of the system. Then we can write
𝑑 𝑑
𝑥,
ො 𝑝Ƹ𝑥 𝜓 𝑥 = 𝑥ො 𝑝Ƹ𝑥 − 𝑝Ƹ𝑥 𝑥ො 𝜓 𝑥 = 𝑥 −𝑖ℏ 𝜓 𝑥 − −𝑖ℏ 𝑥𝜓(𝑥)
𝑑𝑥 𝑑𝑥
𝑑𝜓 𝑥 𝑑𝜓 𝑥
= −𝑖ℏ 𝑥 + 𝑖ℏ𝜓 𝑥 + 𝑖ℏ 𝑥
𝑑𝑥 𝑑𝑥
= 𝑖ℏ 𝜓 𝑥

This implies that 𝑥,

ො 𝑝Ƹ𝑥 = 𝑖ℏ
 Operators in Quantum Mechanics

Solution: (b) Using the wavefuction 𝜓 𝑥 we can write

𝑑 𝑑
𝑥,
ො 𝑝Ƹ𝑦 𝜓 𝑥 = 𝑥ො 𝑝Ƹ𝑦 − 𝑝Ƹ𝑦 𝑥ො 𝜓 𝑥 = 𝑥 −𝑖ℏ 𝜓 𝑥 − −𝑖ℏ 𝑥𝜓(𝑥)
𝑑𝑦 𝑑𝑦
𝑑𝜓 𝑥 𝑑𝜓 𝑥
= −𝑖ℏ 𝑥 + 0 + 𝑖ℏ 𝑥
𝑑𝑦 𝑑𝑦
=0

This implies that 𝑥,

ො 𝑝Ƹ𝑦 = 0