Lecture #22

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
11 One Dimensional Problems: 1-D infinite potential well, 1-D finite potential well, and quantum 2.5
mechanical tunneling.
12 Particle in 1-D lattice, Kronig-Penney Model and the E/k Diagram. 2

1
Recap
• Time-independent Schrodinger equation for a free particle • Stationary state
𝑖𝐸𝑡
ℏ2 𝑑 2 𝜓 −
− + 𝑉(𝑥)𝜓 = 𝐸𝜓 Ψ 𝑥, 𝑡 = 𝜓 𝑥 𝑒 ℏ
2𝑚 𝑑𝑥 2
Ψ 𝑥, 𝑡 2 = Ψ ∗ 𝑥, 𝑡 Ψ 𝑥, 𝑡
2 2
ℏ 𝑑 𝜓
− = 𝐸𝜓 𝑖𝐸𝑡 ∗ 𝑖𝐸𝑡
2𝑚 𝑑𝑥 2 − −
= 𝜓 𝑥 𝑒 ℏ 𝜓 𝑥 𝑒 ℏ
2𝑚𝐸
𝜓 𝑥 = 𝐴𝑒 𝑖𝑘𝑥 + 𝐵𝑒 −𝑖𝑘𝑥 𝑘=
ℏ = 𝜓∗ 𝑥 𝜓 𝑥 = 𝜓 𝑥 2

𝑖𝐸𝑡 𝐸
Ψ 𝑥, 𝑡 = 𝜓 𝑥 −
𝑒 ℏ = 𝐴𝑒 𝑖 𝑘𝑥−𝜔𝑡
+ 𝐵𝑒 −𝑖 𝑘𝑥+𝜔𝑡 ω=
ℏ

𝑘 > 0 → Wave travelling to the right; 𝑘 < 0 → Wave travelling to the left; no
Ψk 𝑥, 𝑡 = 𝐴𝑒 𝑖 𝑘𝑥−𝜔𝑡
restrictions on 𝑘
∞ ∞
න Ψ𝑘∗ 𝑥, 𝑡 Ψ𝑘 𝑥, 𝑡 𝑑𝑥 = 𝐴 2
න 𝑑𝑥 → ∞ → Wavefunction cannot be normalized
−∞ −∞

1 ∞
Ψ 𝑥, 𝑡 = ‫׬‬ 𝜙 𝑘 𝑒 𝑖(𝑘𝑥−𝜔𝑡) 𝑑𝑘 → Now this can be normalized 2
2𝜋 −∞
 Schrodinger Equation and Applications
Infinite square well/Particle in a box “bound states”
0, if 0 ≤ 𝑥 ≤ 𝑎
The particle is in the potential well, such that 𝑉 𝑥 = ቊ
∞, otherwise
Find: I II III
(a) Wave function of the particle, 𝜓(𝑥)
(b) Energy of the particle, E
(c) Time evolved wave function, Ψ(𝑥, 𝑡)

3
 Schrodinger Equation and Applications
Infinite square well/Particle in a box “bound states”
0, if 0 ≤ 𝑥 ≤ 𝑎
The particle is in the potential well, such that 𝑉 𝑥 = ቊ
∞, otherwise
Find: I II III
(a) Wave function of the particle, 𝜓(𝑥)
(b) Energy of the particle, E
(c) Time evolved wave function, Ψ(𝑥, 𝑡)

• The time independent Schrodinger equation in region II is

In region I and III wave
ℏ2 𝑑 2 𝜓 function is zero because
− = 𝐸𝜓 infinite potential
2𝑚 𝑑𝑥 2

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

4
 Schrodinger Equation and Applications
Infinite square well/Particle in a box “bound states”
0, if 0 ≤ 𝑥 ≤ 𝑎
The particle is in the potential well, such that 𝑉 𝑥 = ቊ
∞, otherwise
Find: I II III
(a) Wave function of the particle, 𝜓(𝑥)
(b) Energy of the particle, E
(c) Time evolved wave function, Ψ(𝑥, 𝑡)

• The time independent Schrodinger equation in region II is

In region I and III wave
ℏ2 𝑑 2 𝜓 function is zero because
− = 𝐸𝜓 infinite potential
2𝑚 𝑑𝑥 2

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

• Let us assume the solution of this equation in the form

𝜓 𝑥 = 𝐴 sin 𝑘𝑥 + 𝐵 cos 𝑘𝑥, where A and B are the constants
5
 Schrodinger Equation and Applications
• At boundary, the wave function must vanish. That is, it should satisfy

𝜓 0 =0 → BC 1 and
𝜓 𝑎 =0 → BC(2)

6
 Schrodinger Equation and Applications
• At boundary, the wave function must vanish. That is, it should satisfy

𝜓 0 =0 → BC 1 and
𝜓 𝑎 =0 → BC(2)
• Using BC(1) we get: 𝜓 0 = 𝐴 sin 0 + 𝐵 cos 0 = 0 ⇒ 𝐵 = 0
𝑚𝜋
Using BC(2) we get: 𝜓 𝑎 = 𝐴 sin 𝑘𝑎 = 0 ⇒ 𝑘𝑎 = ±𝑚𝜋 ⇒ 𝑘 = ± , where m = 0, 1, 2, 3 …..
𝑎

7
 Schrodinger Equation and Applications
• At boundary, the wave function must vanish. That is, it should satisfy

𝜓 0 =0 → BC 1 and
𝜓 𝑎 =0 → BC(2)
• Using BC(1) we get: 𝜓 0 = 𝐴 sin 0 + 𝐵 cos 0 = 0 ⇒ 𝐵 = 0
𝑚𝜋
Using BC(2) we get: 𝜓 𝑎 = 𝐴 sin 𝑘𝑎 = 0 ⇒ 𝑘𝑎 = ±𝑚𝜋 ⇒ 𝑘 = ± , where m = 0, 1, 2, 3 …..
𝑎

• By dropping 𝑘 = 0 as it gives 𝜓 𝑥 = 0 and all negative values (they give the same solutions as
positive k values), the distinct solutions correspond to
𝑛𝜋
𝑘= + , where n = 1, 2, 3 …..
𝑎

8
 Schrodinger Equation and Applications
• At boundary, the wave function must vanish. That is, it should satisfy

𝜓 0 =0 → BC 1 and
𝜓 𝑎 =0 → BC(2)
• Using BC(1) we get: 𝜓 0 = 𝐴 sin 0 + 𝐵 cos 0 = 0 ⇒ 𝐵 = 0
𝑚𝜋
Using BC(2) we get: 𝜓 𝑎 = 𝐴 sin 𝑘𝑎 = 0 ⇒ 𝑘𝑎 = ±𝑚𝜋 ⇒ 𝑘 = ± , where m = 0, 1, 2, 3 …..
𝑎

• By dropping 𝑘 = 0 as it gives 𝜓 𝑥 = 0 and all negative values (they give the same solutions as
positive k values), the distinct solutions correspond to
𝑛𝜋
𝑘= + , where n = 1, 2, 3 …..
𝑎
• Then we can write the wave function and energy of the particle as

𝑛𝜋𝑥 k2 ℏ2 𝑛 2 𝜋 2 ℏ2
𝜓𝑛 𝑥 = 𝐴 sin 𝑘𝑥 = 𝐴 sin and En = =
𝑎 2𝑚 2𝑚𝑎2
9
 Schrodinger Equation and Applications
• We can calculate the normalization constant A as
𝑎 𝑎 𝑎 2
‫׬‬0 𝜓 ∗ 𝑥 𝜓 𝑥 𝑑𝑥 = 1 ⇒ ‫׬‬0 𝐴 2 sin2 𝑘𝑥 𝑑𝑥 = 1 ⇒ 𝐴 2 × =1⇒𝐴=
2 𝑎

(we choose the positive real root of A; negative sign of A has no special significance)

10
 Schrodinger Equation and Applications
• We can calculate the normalization constant A as
𝑎 𝑎 𝑎 2
‫׬‬0 𝜓 ∗ 𝑥 𝜓 𝑥 𝑑𝑥 = 1 ⇒ ‫׬‬0 𝐴 2 sin2 𝑘𝑥 𝑑𝑥 = 1 ⇒ 𝐴 2 × =1⇒𝐴=
2 𝑎

(we choose the positive real root of A, negative sign of A has no special significance)
• Therefore, the wave function of the particle is
2 𝑛𝜋𝑥
𝜓𝑛 𝑥 = sin where: n = 1, 2, 3, 4, … .
𝑎 𝑎

11
 Schrodinger Equation and Applications
• We can calculate the normalization constant A as
𝑎 𝑎 𝑎 2
‫׬‬0 𝜓 ∗ 𝑥 𝜓 𝑥 𝑑𝑥 = 1 ⇒ ‫׬‬0 𝐴 2 sin2 𝑘𝑥 𝑑𝑥 = 1 ⇒ 𝐴 2 × =1⇒𝐴=
2 𝑎

(we choose the positive real root of A, negative sign of A has no special significance)
• Therefore, the wave function of the particle is
2 𝑛𝜋𝑥
𝜓𝑛 𝑥 = sin where: n = 1, 2, 3, 4, … .
𝑎 𝑎

• This gives an infinite set of solutions:

2 𝜋𝑥 𝜋 2 ℏ2
𝜓1 𝑥 = sin ; 𝐸1 =
𝑎 𝑎 2𝑚𝑎2

2 2𝜋𝑥 4𝜋 2 ℏ2
𝜓2 𝑥 = sin ; 𝐸2 =
𝑎 𝑎 2𝑚𝑎2
2 3𝜋𝑥 9𝜋2 ℏ2
𝜓3 𝑥 = sin ; 𝐸3 = , and so on.
𝑎 𝑎 2𝑚𝑎2
12
 Schrodinger Equation and Applications
• We can calculate the normalization constant A as
𝑎 𝑎 𝑎 2
‫׬‬0 𝜓 ∗ 𝑥 𝜓 𝑥 𝑑𝑥 = 1 ⇒ ‫׬‬0 𝐴 2 sin2 𝑘𝑥 𝑑𝑥 = 1 ⇒ 𝐴 2 × =1⇒𝐴=
2 𝑎

(we choose the positive real root of A, negative sign of A has no special significance)
• Therefore, the wave function of the particle is
2 𝑛𝜋𝑥
𝜓𝑛 𝑥 = sin where: n = 1, 2, 3, 4, … .
𝑎 𝑎

• This gives an infinite set of solutions:

2 𝜋𝑥 𝜋 2 ℏ2
𝜓1 𝑥 = sin ; 𝐸1 =
𝑎 𝑎 2𝑚𝑎2

2 2𝜋𝑥 4𝜋 2 ℏ2
𝜓2 𝑥 = sin ; 𝐸2 =
𝑎 𝑎 2𝑚𝑎2
2 3𝜋𝑥 9𝜋2 ℏ2
𝜓3 𝑥 = sin ; 𝐸3 = , and so on.
𝑎 𝑎 2𝑚𝑎2
" → 𝜓1 , 𝜓2 , 𝜓3 … . represent the ground state, first excited, second excited state, … … . " 13
 Schrodinger Equation and Applications
• Let us sketch the wave functions and corresponding energy

(wave function) (probability) (energy level)

→ Wave functions are continuous

→ Confined quantum mechanical systems have discrete energies

→ Represents an example of “bound” quantum system.

14
Estimating ground state energy from uncertainty principle
→Position uncertainty
∆𝑥 = 𝑎

→Minimum momentum uncertainty

ℏ
∆𝑝 =
2𝑎

→If we want to localize the particle, the particle

will get the finite momentum
ℏ
𝑝𝑚𝑖𝑛 = • Actual ground
2𝑎
state energy:
→ Minimum kinetic energy
𝜋 2 ℏ2
𝑝2 ℏ2 𝐸1 =
= 2𝑚𝑎2
2𝑚 8𝑚𝑎2
15
 Schrodinger Equation and Applications
• The wave function solutions are orthonormal

‫𝑛𝑚𝛿 = 𝑥𝑑 𝑥 𝑛𝜓 ∗ 𝑥 𝑚𝜓 ׬‬
Kronecker delta

• The wave function solutions form a complete set: Any function f(x) can be expressed as
∞ ∞
2 𝑛 𝜋𝑥
𝑓 𝑥 = ෍ 𝑐𝑛 𝜓𝑛 (𝑥) = ෍ 𝑐𝑛 sin( )
𝑎 𝑎
𝑛=1 𝑛=1

where
∞ ∞

න𝜓𝑚 𝑥 ∗ 𝑓 𝑥 𝑑𝑥 = ෍ 𝑐𝑛 න 𝜓𝑚 𝑥 ∗ 𝜓𝑛 𝑥 𝑑𝑥 = ෍ 𝑐𝑛 𝛿𝑚𝑛 = 𝑐𝑚
𝑛=1 𝑛=1
16
 Schrodinger Equation and Applications
• We can write the initial wave function as a linear combination
2 𝑛𝜋𝑥
Ψ 𝑥, 0 = σ∞ 𝑐 𝜓
𝑛=1 𝑛 𝑛 𝑥 = σ ∞
𝑛=1 𝑐𝑛 sin
𝑎 𝑎

2 𝑎 𝑛𝜋𝑥
Where, 𝑐𝑛 = < 𝜓𝑛 |Ψ > = ‫׬‬0 sin 𝑎 Ψ 𝑥, 0 𝑑𝑥
𝑎

17
 Schrodinger Equation and Applications
• We can write the initial wave function as a linear combination
2 𝑛𝜋𝑥
Ψ 𝑥, 0 = σ∞ 𝑐 𝜓
𝑛=1 𝑛 𝑛 𝑥 = σ ∞
𝑛=1 𝑐𝑛 sin
𝑎 𝑎

2 𝑎 𝑛𝜋𝑥
Where, 𝑐𝑛 = < 𝜓𝑛 |Ψ > = ‫׬‬0 sin 𝑎 Ψ 𝑥, 0 𝑑𝑥
𝑎

• The stationary states are then written as

𝑛2 𝜋2 ℏ
2 𝑛𝜋𝑥 −𝑖 𝑡
2𝑚𝑎2
𝜓𝑛 𝑥, 𝑡 = sin 𝑒
𝑎 𝑎

18
 Schrodinger Equation and Applications
• We can write the initial wave function as a linear combination
2 𝑛𝜋𝑥
Ψ 𝑥, 0 = σ∞ 𝑐 𝜓
𝑛=1 𝑛 𝑛 𝑥 = σ ∞
𝑛=1 𝑐𝑛 sin
𝑎 𝑎

2 𝑎 𝑛𝜋𝑥
Where, 𝑐𝑛 = < 𝜓𝑛 |Ψ > = ‫׬‬0 sin 𝑎 Ψ 𝑥, 0 𝑑𝑥
𝑎

• The stationary states are then written as

𝑛2 𝜋2 ℏ
2 𝑛𝜋𝑥 −𝑖 𝑡
2𝑚𝑎2
𝜓𝑛 𝑥, 𝑡 = sin 𝑒
𝑎 𝑎

• The most general solution of the time-dependent Schrodinger equation is then

∞ ∞ 𝑛2 𝜋2 ℏ
2 𝑛𝜋𝑥 −𝑖
2𝑚𝑎2
𝑡
Ψ 𝑥, 𝑡 = ෍ 𝑐𝑛 𝜓𝑛 𝑥, 𝑡 = ෍ 𝑐𝑛 sin 𝑒
𝑎 𝑎
𝑛=1 𝑛=1

19
 Schrodinger Equation and Applications
Example Problem: A particle of mass m moves freely inside an infinite potential well of
length a. Initially (at t=0), the particle is in the state
3 3𝜋𝑥 1 5𝜋𝑥
Ψ 𝑥, 0 = sin + sin
5𝑎 𝑎 5𝑎 𝑎

Find Ψ 𝑥, 𝑡 at any later time t.

20
 Schrodinger Equation and Applications
Example Problem: A particle of mass m moves freely inside an infinite potential well of
length a. Initially (at t=0), the particle is in the state
3 3𝜋𝑥 1 5𝜋𝑥
Ψ 𝑥, 0 = sin + sin
5𝑎 𝑎 5𝑎 𝑎

Find Ψ 𝑥, 𝑡 at any later time t.

Solution: For a particle in an infinite box of length a
2 𝑛𝜋𝑥
𝜓𝑛 𝑥 = sin where: n = 1, 2, 3, 4, … .
𝑎 𝑎
𝑛 2 𝜋 2 ℏ2
En =
2𝑚𝑎2

21
 Schrodinger Equation and Applications
Example Problem: A particle of mass m moves freely inside an infinite potential well of
length a. Initially (at t=0), the particle is in the state
3 3𝜋𝑥 1 5𝜋𝑥
Ψ 𝑥, 0 = sin + sin
5𝑎 𝑎 5𝑎 𝑎

Find Ψ 𝑥, 𝑡 at any later time t.

Solution: For a particle in an infinite box of length a
2 𝑛𝜋𝑥
𝜓𝑛 𝑥 = sin where: n = 1, 2, 3, 4, … .
𝑎 𝑎
𝑛 2 𝜋 2 ℏ2
En =
2𝑚𝑎2

Using this wave function we can write

3 3𝜋𝑥 1 5𝜋𝑥 3 1
Ψ 𝑥, 0 = sin + sin = 𝜓 𝑥 + 𝜓 𝑥
5𝑎 𝑎 5𝑎 𝑎 10 3 10 5

𝑖𝐸 𝑡
− ℏ𝑛
We can write the time-dependent wavefunction as Ψ 𝑥, 𝑡 = σ 𝑐𝑛 𝜓𝑛 𝑥, 0 𝑒 22
 Schrodinger Equation and Applications

3 𝑖𝐸 𝑡
− 3 1 𝑖𝐸 𝑡
− 5
Ψ 𝑥, 𝑡 = 𝜓3 𝑥 𝑒 ℏ + 𝜓5 𝑥 𝑒 ℏ
10 10

9𝜋 2 ℏ2
Where, E3 =
2𝑚𝑎2
25𝜋2 ℏ2
E5 =
2𝑚𝑎2

23
 Schrodinger Equation and Applications
Example Problem: A particle which is confined to move in a one-dimensional region
𝜋𝑥
0 ≤ 𝑥 ≤ 𝑎 is represented by the wavefunction Ψ 𝑥, 𝑡 = sin exp −𝑖𝜔𝑡 . Then
𝑎
(a) Find the potential V(x)
a 3𝑎
(b) Calculate the probability of finding the particle in the interval ≤𝑥≤
4 4
Solution:

24
 Schrodinger Equation and Applications
Example Problem: A particle which is confined to move in a one-dimensional region
𝜋𝑥
0 ≤ 𝑥 ≤ 𝑎 is represented by the wavefunction Ψ 𝑥, 𝑡 = sin exp −𝑖𝜔𝑡 . Then
𝑎
(a) Find the potential V(x)
a 3𝑎
(b) Calculate the probability of finding the particle in the interval ≤𝑥≤
4 4
Solution: (a) We know that the time-dependent Schrodinger equation is
𝜕Ψ 𝑥,𝑡 ℏ2 𝜕2 Ψ 𝑥,𝑡
𝑖ℏ = − + 𝑉 𝑥 Ψ x, t
𝜕𝑡 2𝑚 𝜕𝑥 2

𝜕Ψ 𝑥,𝑡 𝜋𝑥
From the given wavefunction, we can calculate: = −𝑖𝜔 sin exp −𝑖𝜔𝑡 = −𝑖𝜔 Ψ 𝑥, 𝑡 ,
𝜕𝑡 𝑎

𝜕2 Ψ 𝑥,𝑡 𝜋 2
and =− Ψ 𝑥, 𝑡
𝜕𝑥 2 𝑎

We can now write

ℏ2 𝜋2
𝑖ℏ −𝑖𝜔 Ψ 𝑥, 𝑡 = − − 2 Ψ 𝑥, 𝑡 + 𝑉 𝑥 Ψ x, t
2𝑚 𝑎
ℏ2 𝜋 2
⇒ 𝑉 𝑥 = ℎ𝜔 − 25
2𝑚𝑎2
 Schrodinger Equation and Applications
(b) We can write the probability as

3𝑎 3𝑎
‫𝑎׬‬4 Ψ ∗ 𝑥, 𝑡 Ψ 𝑥, 𝑡 𝑑𝑥 ‫𝑎׬‬4 𝜓 ∗ 𝑥 𝜓 𝑥 𝑑𝑥
4 4
𝑃= 𝑎 ∗ = 𝑎 ∗
‫׬‬0 Ψ 𝑥, 𝑡 Ψ 𝑥, 𝑡 𝑑𝑥 ‫׬‬0 𝜓 𝑥 𝜓 𝑥 𝑑𝑥

3𝑎
𝜋𝑥
‫𝑎׬‬4 sin2 𝑎
𝑑𝑥
4 𝜋+2
⇒ 𝑎 𝜋𝑥 = = 0.82
‫׬‬0 sin2 𝑑𝑥 2𝜋
𝑎

26