Module Part II – Quantum Mechanics No.

of
no. lectures
7 Birth of Quantum Mechanics: particle aspect of radiation (blackbody radiation, photoelectric 3
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
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. 2

1
Recap
• Time-dependent Schrodinger equation is

𝜕Ψ 𝑥, 𝑡 ℏ2 𝜕 2 Ψ 𝑥, 𝑡 Assumption: Potential is
𝑖ℏ =− 2
+ 𝑉 𝑥 Ψ x, t time-independent
𝜕𝑡 2𝑚 𝜕𝑥

• Solution of time-dependent Schrodinger equation

Ψ 𝑥, 𝑡 = 𝜓 𝑥 𝜙(𝑡)

𝑑𝜙 𝑖𝐸 ℏ2 𝑑 2 𝜓
=− 𝜙 and − + 𝑉𝜓 = 𝐸𝜓
𝑑𝑡 ℏ 2𝑚 𝑑𝑥 2

• Therefore, the actual time dependent wave function is

𝑖𝐸𝑡
Ψ 𝑥, 𝑡 = 𝜓 𝑥 𝑒− ℏ

2
 Schrodinger Equation and Applications
• Therefore, the actual time dependent wave function is “stationary states”

𝑖𝐸𝑡
−
Ψ 𝑥, 𝑡 = 𝜓 𝑥 𝑒 ℏ

This is called the stationary state solution of the time-dependent Schrodinger equation

→ if potential is time independent, the time evolution of a wave function is simply the
𝑖𝐸𝑡
product of 𝜓 𝑥 and a factor 𝑒− ℏ

3
 Schrodinger Equation and Applications
• Therefore, the actual time dependent wave function is “stationary states”

𝑖𝐸𝑡
−
Ψ 𝑥, 𝑡 = 𝜓 𝑥 𝑒 ℏ

This is called the stationary state solution of the time-dependent Schrodinger equation

→ if potential is time independent, the time evolution of a wave function is simply the
𝑖𝐸𝑡
product of 𝜓 𝑥 and a factor 𝑒− ℏ
• “Stationary state” because the probability density
𝑖𝐸𝑡 ∗ 𝑖𝐸𝑡
−ℏ
Ψ 𝑥, 𝑡 2 = Ψ∗ 𝑥, 𝑡 Ψ 𝑥, 𝑡 = 𝜓 𝑥 𝑒 𝜓 𝑥 𝑒− ℏ = 𝜓∗ 𝑥 𝜓 𝑥 = 𝜓 𝑥 2

Ψ 𝑥, 𝑡 is
→ probability density is independent of time (assuming E is real) normalizable
(Homework: every expectation value is constant in time) only if E is real
• “Stationary states” have definite energy
෡Ψ=EΨ
𝐻 ෡ =𝐸
𝐻 ෡2⟩ = 𝐸2
⟨𝐻
4
 Schrodinger Equation and Applications
• In the case of an infinite set of solutions
𝜓1 𝑥 , 𝜓2 𝑥 , 𝜓3 𝑥 , … . . associated with energy E1 , E2 , E3 , … . ., respectively:
The total wave function

𝜓 𝑥 = 𝑐1 𝜓1 𝑥 + 𝑐2 𝜓2 𝑥 + 𝑐3 𝜓3 𝑥 + … . . = σ∞
𝑛=1 𝑐𝑛 𝜓𝑛 𝑥

where, 𝑐𝑛 = ‫𝑥𝑑 𝑥 𝜓 𝑥 ∗𝑛𝜓 ׬‬

• Now, the full time-dependent wave function is

∞
𝑖𝐸 𝑡
− 𝑛
Ψ 𝑥, 𝑡 = ෍ 𝑐𝑛 𝜓𝑛 𝑥 𝑒 ℏ
𝑛=1

→ Ψ 𝑥, 𝑡 here is NOT stationary in general as different 𝜓 ′ 𝑠 have different energy.

5
 Schrodinger Equation and Applications
The Free Particle “V(x) = 0; No boundaries; continuous energy states”
• The time independent Schrodinger equation is

ℏ2 𝑑 2 𝜓
− = 𝐸𝜓
2𝑚 𝑑𝑥 2

𝑑2𝜓 2𝑚𝐸
⇒ = −𝑘 2 𝜓 , where 𝑘 = Eq.(1)
𝑑𝑥 2 ℏ

6
 Schrodinger Equation and Applications
The Free Particle “V(x) = 0; No boundaries; continuous energy states”
• The time independent Schrodinger equation is

ℏ2 𝑑 2 𝜓
− = 𝐸𝜓
2𝑚 𝑑𝑥 2

𝑑2𝜓 2𝑚𝐸
⇒ = −𝑘 2 𝜓 , where 𝑘 = Eq.(1)
𝑑𝑥 2 ℏ

• Let us choose the solution in a general form

𝜓 𝑥 = 𝐴𝑒 𝑖𝑘𝑥 + 𝐵𝑒 −𝑖𝑘𝑥 Eq.(2) (A and B are the constants)

“there are no boundary conditions for wave function”

⇒ no restrictions on the values of 𝑘
⇒ no restrictions on the energy particle can carry“
ℏ2 𝑘 2
⇒ it can have any positive energy 𝐸 =
2𝑚
7
 Schrodinger Equation and Applications
The Free Particle “V(x) = 0; No boundaries; continuous energy states”
• Now, the time dependent wave function (the stationary state) we can write as

𝑖𝐸𝑡 ℏ𝑘2 ℏ𝑘2

− 𝑖 𝑘𝑥− 𝑡 −𝑖 𝑘𝑥+ 𝑡
Ψ 𝑥, 𝑡 = 𝜓 𝑥 𝑒 ℏ = 𝐴𝑒 2𝑚 + 𝐵𝑒 2𝑚 ℏ 𝑘2 𝐸 2𝜋𝐸
Where: = = = 2𝜋𝑣 = 𝜔
2𝑚 ℏ ℎ

= 𝐴𝑒 𝑖 𝑘𝑥−𝜔𝑡 + 𝐵𝑒 −𝑖 𝑘𝑥+𝜔𝑡
 Schrodinger Equation and Applications
The Free Particle “V(x) = 0; No boundaries; continuous energy states”
• Now, the time dependent wave function (the stationary state) we can write as

𝑖𝐸𝑡 ℏ𝑘2 ℏ𝑘2

− 𝑖 𝑘𝑥− 𝑡 −𝑖 𝑘𝑥+ 𝑡
Ψ 𝑥, 𝑡 = 𝜓 𝑥 𝑒 ℏ = 𝐴𝑒 2𝑚 + 𝐵𝑒 2𝑚 ℏ 𝑘2 𝐸 2𝜋𝐸
Where: = = = 2𝜋𝑣 = 𝜔
2𝑚 ℏ ℎ

= 𝐴𝑒 𝑖 𝑘𝑥−𝜔𝑡 + 𝐵𝑒 −𝑖 𝑘𝑥+𝜔𝑡

“A wave traveling to the right “A wave traveling to the left “→ stationary states of free
2𝜋 + 2𝜋 = particle are the propagating
with wavelength 𝜆 = ” with wavelength 𝜆 = ”
𝑘 𝑘 plane waves”
 Schrodinger Equation and Applications
The Free Particle “V(x) = 0; No boundaries; continuous energy states”
• Now, the time dependent wave function (the stationary state) we can write as

𝑖𝐸𝑡 ℏ𝑘2 ℏ𝑘2

− 𝑖 𝑘𝑥− 𝑡 −𝑖 𝑘𝑥+ 𝑡
Ψ 𝑥, 𝑡 = 𝜓 𝑥 𝑒 ℏ = 𝐴𝑒 2𝑚 + 𝐵𝑒 2𝑚 ℏ 𝑘2 𝐸 2𝜋𝐸
Where: = = = 2𝜋𝑣 = 𝜔
2𝑚 ℏ ℎ

= 𝐴𝑒 𝑖 𝑘𝑥−𝜔𝑡 + 𝐵𝑒 −𝑖 𝑘𝑥+𝜔𝑡

“A wave traveling to the right “A wave traveling to the left “→ stationary states of free
2𝜋 + 2𝜋 = particle are the propagating
with wavelength 𝜆 = ” with wavelength 𝜆 = ”
𝑘 𝑘 plane waves”.

• We can also write in a simple form by combining the two terms as

2𝑚𝐸
Ψk 𝑥, 𝑡 = 𝐴𝑒 𝑖 𝑘𝑥−𝜔𝑡 , with 𝑘 = ±
ℏ
→ k>0: wave is travelling to the right
→ k<0: wave is travelling to the left
 Schrodinger Equation and Applications
Important Paradoxes “V(x) = 0; No boundaries”
1. The probability density

2 2
P 𝑥, 𝑡 = Ψ𝑘 𝑥, 𝑡 = 𝐴

→ that is, probability is independent of position and time

→ this implies that there is a complete loss of information about position and time of the state. This
ℏ2 𝑘 2
is due to “definite” values of momentum (𝑝 = ℏ𝑘) and energy (E = ), respectively
2𝑚
 Schrodinger Equation and Applications
Important Paradoxes “V(x) = 0; No boundaries”
1. The probability density

2 2
P 𝑥, 𝑡 = Ψ𝑘 𝑥, 𝑡 = 𝐴

→ that is, probability is independent of position and time

→ this implies that there is a complete loss of information about position and time of the state. This
ℏ2 𝑘 2
is due to “definite” values of momentum (𝑝 = ℏ𝑘) and energy (E = ), respectively
2𝑚

𝜔 𝐸 ℏ 𝐸
2. The speed of the wave vwave = = × =
𝑘 ℏ 2𝑚𝐸 2𝑚

2𝐸
The speed of a free particle vparticle = ⇒ 𝑣𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 = 2 𝑣𝑤𝑎𝑣𝑒 OR 𝑣𝑐𝑙𝑎𝑠𝑠𝑖𝑐𝑎𝑙 = 2 𝑣𝑞𝑢𝑎𝑛𝑡𝑢𝑚
𝑚

→ “this means that the particle travels twice as fast as the wave that represents it”
 Schrodinger Equation and Applications
Important Paradoxes “V(x) = 0; No boundaries”

3. Let us normalize the wave function

∞ ∞
‫׬‬−∞ Ψ𝑘∗ 𝑥, 𝑡 Ψ𝑘 𝑥, 𝑡 𝑑𝑥 = 𝐴 2
‫׬‬−∞ 𝑑𝑥 →∞

→ that is, wave function of free particle is not normalizable

→ this implies that Ψ𝑘 𝑥, 𝑡 is not a physical state. That is, a free particle cannot
exist in a stationary state.
→ this also implies that a free particle cannot have a definite momenta and energy
 Schrodinger Equation and Applications
Resolution of Paradoxes
“wave packets NOT a plane wave
• The physical solution to free particle Schrodinger equation is represented by “wave packets” (not
plane waves) defined as

1 ∞
Ψ 𝑥, 𝑡 = ‫𝜙 ׬‬ 𝑘 𝑒 𝑖(𝑘𝑥−𝜔𝑡) 𝑑𝑘 , (free particle’s wave function)
2𝜋 −∞

𝜙 𝑘 represents the amplitude of the wave packets, and is obtained using the initial wave function
Ψ 𝑥, 0 using
1 ∞ This follows from Plancherel’s theorem
𝜙 𝑘 = ‫׬‬−∞ Ψ 𝑥, 0 𝑒 −𝑖𝑘𝑥 𝑑𝑥
2𝜋 (see problem 2.20, Griffiths, 2nd edition)
 Schrodinger Equation and Applications
Resolution of Paradoxes
“wave packets NOT a plane wave”
• The physical solution to free particle Schrodinger equation is represented by “wave packets” (not
plane waves) defined as

1 ∞
Ψ 𝑥, 𝑡 = ‫𝜙 ׬‬ 𝑘 𝑒 𝑖(𝑘𝑥−𝜔𝑡) 𝑑𝑘 , (free particle’s wave function)
2𝜋 −∞

𝜙 𝑘 represents the amplitude of the wave packets, and is obtained using the initial wave function
Ψ 𝑥, 0 using
1 ∞ This follows from Plancherel’s theorem
𝜙 𝑘 = ‫׬‬−∞ Ψ 𝑥, 0 𝑒 −𝑖𝑘𝑥 𝑑𝑥
2𝜋 (see problem 2.20, Griffiths, 2nd edition)

what does the above wave packet solution tell us?

→the position, momentum (or energy) of the particle are no longer known exactly
2𝐸
→the wave packet and the particle travels with the same speed (𝑣𝑔 = ), called the group velocity.
𝑚
→the wave packet is normalizable
Phase and Group Velocities
We know that the velocity of an EM wave in a medium is

1
𝑣=
𝜇𝜖

o If 𝜇 and 𝜖 of a medium does not depend on the frequency of the EM wave, the medium is
called a non-dispersive medium.
→ vacuum is an example of a non-dispersive medium”

In this case the EM wave travels at constant speed

𝜔
𝑣𝑝 = , (𝑣𝑝 is the phase velocity)
𝑘

“→ all waves in a wave packet travel with the same

speed leading to no change in the shape of the wave packet”
o If 𝜇 and 𝜖 of a medium depend on the frequency of the EM, the medium is called a
dispersive medium. In this case the EM waves of different frequency travel with
different speeds.
Example: dispersion of light by a prism or a raindrop

o The wave packet as a whole, however, travels with the same

velocity called the group velocity.

𝑑𝜔
𝑣𝑔 = , (𝑣𝑔 is the group velocity)
𝑑𝑘

(Explanation of the first-derivative

formula on page 65, Griffiths, 2nd edition)
 Phase and group velocities
F(x,t)

point traveling with phase velocity point traveling with group velocity
Example Problem: The initial wave function of a free particle is given as
Ψ 𝑥, 0 = 𝐴 𝑒 −𝑎|𝑥| , A and a are positive real constants. Then
(a) Find the value of A
(b) Find the amplitude of wave packets, 𝜙(𝑘)
(c) Find Ψ(𝑥, 𝑡)
(d) Discuss the limiting cases: i) a is very large ii) a is very small
Example Problem: The initial wave function of a free particle is given as
Ψ 𝑥, 0 = 𝐴 𝑒 −𝑎|𝑥| , A and a are positive real constants. Then
(a) Find the value of A
(b) Find the amplitude of wave packets, 𝜙(𝑘)
(c) Find Ψ(𝑥, 𝑡)
(d) Discuss the limiting cases: i) a is very large ii) a is very small

Solution: (a) Since Ψ 𝑥, 0 is a quantum mechanical system wavefunction, it must be normalizable.

⇒ The normalize wave function is Ψ 𝑥, 0 = 𝑎 𝑒 −𝑎|𝑥|

(b) The amplitude of the wave packet is given by
∞
1
𝜙 𝑘 = න Ψ 𝑥, 0 𝑒 −𝑖𝑘𝑥 𝑑𝑥
2𝜋 −∞
(b) The amplitude of the wave packet is given by
∞
1
𝜙 𝑘 = න Ψ 𝑥, 0 𝑒 −𝑖𝑘𝑥 𝑑𝑥
2𝜋 −∞
(c) The time-dependent wave function is
∞
1
Ψ 𝑥, 𝑡 = න 𝜙 𝑘 𝑒 𝑖(𝑘𝑥−𝜔𝑡) 𝑑𝑘
2𝜋 −∞
(c) The time-dependent wave function is
∞
1
Ψ 𝑥, 𝑡 = න 𝜙 𝑘 𝑒 𝑖(𝑘𝑥−𝜔𝑡) 𝑑𝑘
2𝜋 −∞

d) Case I: If a is very large: Ψ 𝑥, 0 will be sharp narrow spike wave function, AND
2
𝜙 𝑘 ≅ ,a broad and flat wave function
𝜋𝑎

→ position of the particle is well-defined but momentum is ill-defined

(c) The time-dependent wave function is
∞
1
Ψ 𝑥, 𝑡 = න 𝜙 𝑘 𝑒 𝑖(𝑘𝑥−𝜔𝑡) 𝑑𝑘
2𝜋 −∞

d) Case I: If a is very large: Ψ 𝑥, 0 will be sharp narrow spike wave function, AND
2
𝜙 𝑘 ≅ ,a broad and flat wave function
𝜋𝑎

→ position of the particle is well-defined but momentum is ill-defined

Case II: If a is very small: Ψ 𝑥, 0 will be broad and flat wave function, AND
2𝑎3 1
𝜙 𝑘 ≅ × , will be sharp narrow spike wave function
𝜋 𝑘2

→ position of the particle is ill-defined but momentum is well defined