Lecture # 6

Module Part II – Quantum Mechanics No. of

no. lectures
7 Birth of Quantum Mechanics: particle aspect of radiation (blackbody radiation, photoelectric 3 + 0.5
effect, Compton effect), wave aspect of particle (de Broglie’s hypothesis, Davisson-Germer
experiment), wave-particle duality, double-slit experiment
8 Quantum Mechanical Wave Function: wave function, representation of wave function, 3 - 0.5
Schrödinger equation, probability density, statistical interpretation, superposition principle,
continuity equation.
9 Quantum Mechanical Operators: observables and operators, linear operators, eigenvalues and 1.5
eigen vectors of operators, Hermitian operators, product of operators, expectation values and
uncertainty relations.
10 Time-Independent Schrodinger Equation: stationary states, free particle solution, bound states 2.5
11 One Dimensional Problems: 1-D infinite potential well, 1-D finite potential well, and quantum 2
mechanical tunneling.
12 Particle in 1-D lattice, Kronig-Penney Model and the E/k Diagram. 1

1
Recap
▪ Ψ 𝑟,
Ԧ 𝑡 → ȁΨ >

▪ ȁΨۧ † = ‫ۦ‬Ψȁ

2
Remark on Dirac notation

▪ Ket vector ȁΨ > represents wave function Ψ 𝑟,

Ԧ𝑡

▪ ȁΨ > is independent of any particular representation

▪ If you want to know the position of a particle, then represent ȁΨ > in coordinate space

Ԧ t ȁΨ > = Ψ 𝑟,
< 𝑟, Ԧ𝑡

▪ If you want to know the momentum of a particle, then represent ȁΨ > in momentum space

Ԧ t ȁΨ > = Ψ 𝑝,
< 𝑝, Ԧ𝑡

3
Properties of kets and bras
▪ Scalar product: The scalar/inner product of two wave functions Ψ1 𝑥 and Ψ2 𝑥 is defined as
∞
Ψ1 𝑥, 𝑡 , Ψ2 𝑥, 𝑡 = ‫׬‬−∞ Ψ1∗ 𝑥, 𝑡 Ψ2 𝑥, 𝑡 𝑑𝑥 → < Ψ1 ȁΨ2 >

→ For a scalar product to exist, we choose only those wave functions for which it is finite.
→ < Ψ1 ȁΨ2 >≠< Ψ2 ȁΨ1 > (not an ordinary vector)
→ < Ψ1 ȁΨ2 >= < Ψ2 ȁΨ1 >∗

▪ Normalized wavefunction:
→ If < Ψ1 ȁΨ1 > = 1, ȁ𝛹1 > is said to be a normalized wave function.
→ < Ψ1 ȁΨ1 > = 0 only for the case when ȁ𝛹1 > = 𝑂 (zero vector)

4
Properties of kets and bras (continuing)

▪ Orthogonal wavefunction:
If < Ψ1 ȁΨ2 >= 0, then Ψ1 > and Ψ2 > is said to be orthogonal to each other.

▪ Orthonormal wave functions: The wavefunction Ψ1 > and Ψ2 > are said to be orthonormal if

< Ψ1 ȁΨ1 >= 1, < Ψ2 ȁΨ2 >= 1, < Ψ1 ȁΨ2 >= 0. < Ψ𝑖 ȁΨ𝑗 >= 𝛿𝑖𝑗

▪ Forbidden quantities: If หΨ1 > and หΨ2 > belong to the same Hilbert space, then

ห𝛹1 > ห𝛹2 > NOTE: If ห𝛹1 > and ห𝛹2 > belong to different Hilbert
Do not make any sense spaces, then the product of ห𝛹1 > and ห𝛹2 > are
< Ψ1 ȁ < Ψ2 ȁ
allowed.
หΨ1 > ⨂หΨ2 > → It is called Tensor product.
หΨ1 > → Example: Spin space
หΨ2 > → Example: Orbital space
5
Properties of kets and bras (continuing)

▪ Tensor product:
หΨ1 >⊗ หΨ2 > → (Ket  Ket) → หΨ1 Ψ2 >

Example:
หΨ1 > = 𝛼 ȁ0 > +𝛽 ȁ1 >
หΨ2 > = 𝛾ȁ0 > +𝛿 ȁ1 >

หΨ1 Ψ2 > = 𝛼 ȁ0 > +𝛽 ȁ1 > ⊗ 𝛾 ȁ0 > +𝛿 ȁ1 >

= 𝛼𝛾ȁ00 > +𝛼𝛿 ȁ01 > +𝛽𝛾ȁ10 > +𝛽𝛿 ȁ11 >

▪ Vector (outer) product:

ȁΨ1 >< Ψ2 ȁ (Ket-Bra) → Operator

6
Problem
หΨ1 > = 2𝑖ห𝜙1 > +ห𝜙2 > −𝑎ห𝜙3 > +4ห𝜙4 >

หΨ2 > = 3ห𝜙1 > −𝑖ห𝜙2 > +5ห𝜙3 > −ห𝜙4 >

Here, ห𝜙1 >, ห𝜙2 >, ห𝜙3 >, and ห𝜙4 > are orthonormal kets

Find the value of 𝑎, so that หΨ1 > and หΨ2 > are orthogonal.

Answer:
< Ψ2 ȁΨ1 > = 0
< Ψ2 ȁ = 3 < 𝜙1 ȁ + 𝑖 < 𝜙2 ȁ + 5 < 𝜙3 ȁ− < 𝜙4 ȁ

< Ψ2 ȁΨ1 > = 3 < 𝜙1 ȁ + 𝑖 < 𝜙2 ȁ + 5 < 𝜙3 ȁ− < 𝜙4 ȁ 2𝑖ห𝜙1 > +ห𝜙2 > −𝑎ห𝜙3 > +4ห𝜙4 >

= 6𝑖 < 𝜙1 ȁ𝜙1 > +𝑖 < 𝜙2 ȁ𝜙2 > −5𝑎 < 𝜙3 ȁ𝜙3 > −4 < 𝜙4 ȁ𝜙4 >

= 7𝑖 − 5𝑎 − 4 = 0 7𝑖 − 4
𝑎=
5 7
The superposition principle

▪ Let’s say 𝜓1 𝑥, 𝑡 , 𝜓2 𝑥, 𝑡 ….. 𝜓𝑛 𝑥, 𝑡 are wavefunctions that individually satisfy Schrodinger’s

equation

→ 𝜓1 𝑥, 𝑡 , 𝜓2 𝑥, 𝑡 ….. 𝜓𝑛 𝑥, 𝑡 are all normalized wavefunctions. For instance

∞
න 𝜓1∗ 𝑥, 𝑡 𝜓1 𝑥, 𝑡 𝑑𝑥 = 1
−∞

→ A quantum mechanical state can also be represented by a superposition of two or more such states.
Ψ 𝑥, 𝑡 = 𝑐1 𝜓1 𝑥, 𝑡 + 𝑐2 𝜓2 𝑥, 𝑡 + . . … . + 𝑐𝑛 𝜓𝑛 𝑥, 𝑡 = σ𝑛𝑖=1 𝑐𝑖 𝜓𝑖 𝑥, 𝑡
Here, 𝑐𝑖 are complex numbers

▪ In Dirac notation: ȁΨ > = σ𝑛𝑖=1 𝑐𝑖 ȁ𝜓𝑖 >

8
The superposition principle (continuing)

▪ ȁΨ > = σ𝑛𝑖=1 𝑐𝑖 ȁ𝜓𝑖 >

▪ Probability of finding the state ȁΨ >

𝑛 𝑛 𝑛
< ΨȁΨ > = ෍ 𝑐𝑖∗ < 𝜓𝑖 ȁ ෍ 𝑐𝑖 ห𝜓𝑖 > = ෍ 𝑐𝑖∗ 𝑐𝑖 < 𝜓𝑖 ȁ𝜓𝑖 >
𝑖=1 𝑖=1 𝑖=1

𝑛
=෍ 𝑐𝑖 2 = 𝑐1 2 + 𝑐2 2 + … + 𝑐𝑛 2
𝑖=1

▪ Here, 𝑐𝑖 2 represents probability of finding the state ȁΨ > in the state ห𝜓𝑖 >

▪ ȁΨ > is a normalized vector, so < ΨȁΨ > = 1. Therefore,

𝑐1 2 + 𝑐2 2 + … + 𝑐𝑛 2 =1

9
More on superposition

▪ In Dirac notation: ȁΨ > = σ𝑛𝑖=1 𝑐𝑖 ȁ𝜓𝑖 >

▪ The probability of finding the particle in a state

→ < 𝜓1 Ψ > =< 𝜓1 σ𝑛𝑖=1 𝑐𝑖 ȁ𝜓𝑖 > = 𝑐1

→ Probability P1 = 𝑐1∗ 𝑐1 = 𝑐1 2
Dimension and basis of a general vector space
▪ Condition for linear independence:
→ Let’s say I have a set of 𝑁 nonzero vectors 𝜙1 , 𝜙2 , 𝜙3 … , 𝜙𝑁 . If these vectors are linear independent,
then they must satisfy the following relationship.
σ𝑁
𝑖=1 𝑎𝑖 𝜙𝑖 = 0, where 𝑎1 = 𝑎2 = 𝑎3 = ⋯ 𝑎𝑁 = 0

▪ Dimension of a vector space:

→ Dimension of a vector space is given by the maximum number of linear independent vectors belonging
to that space.
→ If there are 𝑁 number of linear independent vectors 𝜙1 , 𝜙2 , 𝜙3 … , 𝜙𝑁 , then the dimension of the space
is 𝑁.
→ Any vector 𝜓 in the space can be written as
𝑁

𝜓 = ෍ 𝑎𝑖 𝜙𝑖
𝑖=1
▪ Basis of a vector space:
→ The set of vectors 𝜙1 , 𝜙2 , 𝜙3 … , 𝜙𝑁 , represented as 𝜙𝑖 is called the basis of the vector space.
→ 𝜙1 , 𝜙2 , 𝜙3 … , 𝜙𝑁 are called base vectors.

11
Collapse of wavefunction

▪ ȁΨ > = σ𝑛𝑖=1 𝑐𝑖 ȁ𝜓𝑖 > = 𝑐1 ห𝜓1 > +𝑐2 ห𝜓2 > … . +𝑐𝑛 ห𝜓𝑛 >

▪ When we do an experiment with the quantum system, the entire wavefunction ȁΨ > collapses into
one of the possible states ห𝜓𝑖 >.
→ We only observe that the system is in either of the ห𝜓1 > , ห𝜓2 > or … ห𝜓𝑛 > states.
→ If we wait sufficient time after the measurement, the system represented by ȁΨ > again spreads
out among the many possible statesห𝜓𝑖 >.

▪ Schrödinger’s cat
1 1
ȁ Ψۧ = ȁDead > + ȁAlive >
2 2

→ When you open the box:

ȁΨ > = ȁDead >, or
ȁΨ > = ȁAlive >

12
Problem
ȁΨۧ = 3ȁ𝜙1 ۧ+ ȁ𝜙2 ۧ − 2𝑖 ȁ𝜙3 ۧ; where ȁ𝜙1 ۧ, ȁ𝜙2 ۧ, and ȁ𝜙3 ۧ are orthonormal kets.
(a) Normalize ȁΨۧ
(b) In which probability ȁΨۧ collapses to ȁ𝜙1 ۧ upon a measurement?

13
Problem
ȁ𝜓ۧ = 3𝑖 ȁ𝜙1 ۧ−7𝑖ȁ𝜙2 ۧ and ȁ𝜒ۧ = −ȁ𝜙1 ۧ+2𝑖ȁ𝜙2 ۧ, where ȁ𝜙1 ۧ and ȁ𝜙2 ۧ are orthonormal kets.
Determine ȁ𝜓 + 𝜒ۧ and ‫ 𝜓ۦ‬+ 𝜒ȁ

14
Continuity equation in electricity and magnetism
→ Loss of charge within the enclosure gives rise to 𝐼 = ර 𝐽Ԧ . 𝑑 𝑠Ԧ
current flow from the enclosure to outside

𝑑𝑄 𝜕
𝐼=− = − න 𝜌 𝑟,
Ԧ 𝑡 𝑑𝑉
𝑑𝑡 𝜕𝑡

𝜕
ර 𝐽Ԧ . 𝑑𝑠Ԧ = − න 𝜌 𝑟,
Ԧ 𝑡 𝑑𝑉
𝜕𝑡

𝜕
𝜕𝜌 න 𝛻 . 𝐽Ԧ 𝑑𝑉 = − න 𝜌 𝑟,
Ԧ 𝑡 𝑑𝑉
Ԧ
𝛻. 𝐽 = − 𝜕𝑡
𝜕𝑡
𝜕𝜌
𝛻. 𝐽Ԧ = −
𝜕𝑡

15
Continuity equation in quantum mechanics
▪ One dimensional Schrödinger equation
𝜕Ψ ℏ2 𝜕 2 Ψ
𝑖ℏ =− +𝑉 𝑥 Ψ
𝜕𝑡 2𝑚 𝜕𝑥 2
→ Taking complex conjugate, we get:
𝜕Ψ ∗ ℏ2 𝜕 2 Ψ ∗ ∗
−𝑖ℏ =− + 𝑉 𝑥 Ψ
𝜕𝑡 2𝑚 𝜕𝑥 2

→ Multiplying first eq. with Ψ ∗ and second with Ψ and subtracting, we get:

𝜕Ψ 𝜕Ψ∗ 𝜕 𝜕𝜌
→ L.H.S. 𝑖ℏ Ψ∗ + Ψ = 𝑖ℏ Ψ ∗ Ψ = 𝑖ℏ 𝜌 = Ψ ∗Ψ → Probability density
𝜕𝑡 𝜕𝑡 𝜕𝑡 𝜕𝑡

ℏ2 2
𝜕 Ψ 𝜕 2 Ψ∗ ℏ2 𝜕 𝜕Ψ 𝜕Ψ∗
→ R.H.S. − Ψ∗ 2 − Ψ 2 = − Ψ∗ − Ψ
2𝑚 𝜕𝑥 𝜕𝑥 2𝑚 𝜕𝑥 𝜕𝑥 𝜕𝑥

𝜕𝜌 ℏ2 𝜕 𝜕Ψ 𝜕Ψ∗
→ So, 𝑖ℏ = − Ψ∗ − Ψ
𝜕𝑡 2𝑚 𝜕𝑥 𝜕𝑥 𝜕𝑥
ℏ 𝜕Ψ 𝜕Ψ∗
𝑗= Ψ∗ − Ψ
2𝑖𝑚 𝜕𝑥 𝜕𝑥
𝜕𝑗 𝜕𝜌
=− → Probability current density
𝜕𝑥 𝜕𝑡 16