Lecture-2 Freeparticle and particle in an infinite potential box and finite potential well.

As perturbation theory is the study of the effect of an additional perturbing potential on a system
which has been solved exactly, we need to consider some systems which are exactly solvable. Here
we will discuss the problem of (i) Free particle, (ii) particle in an infinite potential wall one
dimensional box(iii) particle in a well bounded by finite potential barrier (iv) linear harmonic
oscillator (v) particle in a spherically symmetric potential and (vi) hydrogen atom - one electron
atom

Free particle

Force 𝐹⃗ = 0 , Potential energy 𝑈(𝑟⃗) = − ∫ 𝐹⃗ . 𝑑𝑟⃗ = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑎𝑛𝑑 𝑐𝑎𝑛 𝑏𝑒 𝑡𝑎𝑘𝑒𝑛 𝑎𝑠 𝑧𝑒𝑟𝑜

Schrodinger equation is

ℏ2 2
− ∇ 𝜓(𝑟⃗) = 𝜀 𝜓(𝑟⃗)
2𝑚

In one dimension the equation appears as

ℏ2 𝜕 2
− 𝜓(𝑥) = 𝜀 𝜓(𝑥)
2𝑚 𝜕𝑥 2

ℏ2 𝑑 2
− 𝜓(𝑥) = 𝜀𝜓(𝑥)
2𝑚 𝑑𝑥 2

𝑑2 2𝑚𝜀
2 𝜓(𝑥) = − 2 (𝑥)
𝑑𝑥 ℏ

𝑑2
(𝑥) = −𝑘 2 𝜓(𝑥)
𝑑𝑥 2

𝐷2 𝜓(𝑥) = −𝑘 2 𝜓(𝑥)

𝐷2 = −𝑘 2

𝐷 = ±𝑖𝑘

𝐷𝜓(𝑥) = ±𝑖𝑘𝜓(𝑥)

𝑑
𝜓(𝑥) = ±𝑖𝑘𝜓(𝑥)
𝑑𝑥

𝑑𝜓(𝑥)
= ±𝑖𝑘 𝑑𝑥
𝜓(𝑥)

𝑑𝜓(𝑥)
∫ = ± ∫ 𝑖𝑘 𝑑𝑥
𝜓(𝑥)

ln(𝜓(𝑥)) = ±𝑖𝑘 𝑥 + 𝑐

𝜓(𝑥) = 𝐴 𝑒 𝑖𝑘𝑥 + 𝐵𝑒 −𝑖𝑘𝑥

 ℏ2 𝑘 2
𝜀=
2𝑚

Value of k can be obtained from the boundary condition (periodic boundary condition)
x=x+L

𝜓(𝑥) = 𝜓(𝑥 + 𝐿)

A 𝑒 𝑖𝑘𝑥 = A𝑒 𝑖𝑘(𝑥+𝐿) ⟹ 𝑒 𝑖𝑘𝐿 = 1 = 𝑒 𝑖2𝑛𝜋

2𝑛𝜋
𝑖𝑘𝐿 = 𝑖2𝑛𝜋 ; 𝑘=
𝐿

The constants A can be obtained from the normalization condition.

A particle in a one dimensional box

𝐿
A particle of mass m is constrained to move in an infinite potential well of length L with walls at ± 2.

The potential energy for this problem is defined as

𝐿 𝐿
𝑉(𝑥) = {0 𝑓𝑜𝑟 −
2
≤𝑥≤
2
∞ 𝑜𝑡ℎ𝑒𝑟𝑤𝑖𝑠𝑒

The Schrodinger equation appears as

ℏ2 𝜕 2 𝐿 𝐿
− 𝜓(𝑥) = 𝜀 𝜓(𝑥) 𝑓𝑜𝑟 − ≤𝑥≤
2𝑚 𝜕𝑥 2 2 2

𝑑2 2𝑚𝜀
2 𝜓(𝑥) = − 2 𝜓(𝑥)
𝑑𝑥 ℏ
𝑑2 2𝑚𝜀 ℏ2 𝑘 2
𝜓(𝑥) = −𝑘 2 𝜓(𝑥), where 𝑘2 = 𝑜𝑟 𝜀=
𝑑𝑥 2 ℏ2 2𝑚

𝜓(𝑥) = 𝐴 sin 𝑘𝑥 + 𝐵 cos 𝑘𝑥

Now due to infinitely high wall, the probability of the particle out side the well is zero; i.e. the
wave function vanishes at the infinite wall .

Using these boundary conditions we get

 𝜓(𝑥)|𝑥=+𝐿/2 = 0 ⟹ 𝐴 sin(𝑘𝐿/2) + 𝐵 cos(𝑘𝐿/2) = 0

⟹ 𝐴 sin(𝑘𝐿/2) + 𝐵 cos(𝑘𝐿/2) = 0 …. … (1)

Similarly 𝜓(𝑥)|𝑥=−𝐿/2 = 0 ⟹ 𝐴 sin(−𝑘𝐿/2) + 𝐵 cos(−𝑘𝐿/2) = 0

⟹ −𝐴 sin(𝑘𝐿/2) + 𝐵 cos(𝑘𝐿/2) = 0 …. … (2)

Adding Eqn (1) and (2) we get

𝐵 cos(𝑘𝐿/2) = 0 … …. (3)

which imply
𝑛𝜋
either B=0 or cos(𝑘𝐿/2) = 0 = cos 𝑤ℎ𝑒𝑟𝑒 𝑛 𝑖𝑠 𝑎𝑛 𝑜𝑑𝑑 𝑖𝑛𝑡𝑒𝑔𝑒𝑟 = 1,3, ….
2

𝑘𝐿 𝑛𝜋 𝑛𝜋
so either B=0 or = ⟹𝑘=
2 2 𝐿

And subtracting Eqn (2) from Eqn(1) we get

𝐴 sin(𝑘𝐿/2) = 0 … …. (4)

which imply
𝑛𝜋
either A=0 or sin(𝑘𝐿/2) = 0 = sin 𝑤ℎ𝑒𝑟𝑒 𝑛 𝑖𝑠 𝑎𝑛 𝑒𝑣𝑒𝑛 𝑖𝑛𝑡𝑒𝑔𝑒𝑟 = 2,4, …
2

So for the equations (3) and (4) to be simultaneously true, we have two sets of solutions
𝑛𝜋
1) A = 0 and cos(𝑘𝐿/2) = 0 𝑘= , 𝑤ℎ𝑒𝑟𝑒 𝑛 𝑖𝑠 𝑎𝑛 𝑜𝑑𝑑 𝑖𝑛𝑡𝑒𝑔𝑒𝑟 = 1,3, ….
𝐿

𝑛𝜋𝑥 ℏ2 𝑘 2 ℏ2 𝑛 2 𝜋 2 ℏ2 𝑛 2
So that 𝜓(𝑥) = 𝐵 cos 𝑘𝑥 = 𝐵 cos and 𝜀 = = = 8𝑚𝐿2 , n=1,3,5,..
𝐿 2𝑚 2𝑚𝐿2

𝑛𝜋
2) B = 0 and sin(𝑘𝐿/2) = 0 𝑘= , 𝑤ℎ𝑒𝑟𝑒 𝑛 𝑖𝑠 𝑎𝑛 𝑒𝑣𝑒𝑛 𝑖𝑛𝑡𝑒𝑔𝑒𝑟 = 2,4, …
𝐿

𝑛𝜋𝑥 ℏ2 𝑘 2 ℏ2 𝑛 2 𝜋 2 ℏ2 𝑛 2
So that 𝜓(𝑥) = 𝐴 sin 𝑘𝑥 = 𝐴 sin and 𝜀 = = = 8𝑚𝐿2 , n=2,4,6,..
𝐿 2𝑚 2𝑚𝐿2

The value of A and B can be found from the normalization condition

𝐿/2
∫ 𝜓 ⋆ (𝑥)𝜓(𝑥)𝑑𝑥 = 1
−𝐿/2

𝐿/2
⟹ |𝐴|2 ∫ sin 𝑘𝑥 sin 𝑘𝑥 𝑑𝑥 = 1
−𝐿/2

𝐿/2
⟹ |𝐴|2 ∫ sin2 𝑘𝑥 𝑑𝑥 = 1
−𝐿/2

|𝐴|2 𝐿/2
⟹ ∫ (1 − cos 2𝑘𝑥)𝑑𝑥 = 1
2 −𝐿/2
 |𝐴|2 sin 2𝑘𝑥 𝐿/2
⟹ (𝑥 − )| =1
2 2𝑘 −𝐿/2

|𝐴|2 sin 𝑘𝐿 sin −𝑘𝐿

⟹ {(𝐿/2 − ) − (−𝐿/2 − )} = 1
2 2𝑘 2𝑘

|𝐴|2 sin 𝑛𝜋
⟹ (𝐿 − ) = 1 𝑎𝑠 𝑘𝐿 = 𝑛𝜋 𝑎𝑛𝑑 sin 𝑛𝜋 = 0
2 𝑘

|𝐴|2
⟹ 𝐿=1
2

2 2
⟹ 𝐴=√ 𝑠𝑖𝑚𝑖𝑙𝑎𝑟𝑙𝑦 𝐵 = √
𝐿 𝐿

So the bound state levels of the infinite wall box is

Level k and Energy Wave function

number de Broglie 𝑛 2 ℏ2
wave length λ 𝜀=
8𝑚𝐿2

1 𝜋 ℏ2
, 2𝐿 𝜀1 = 2 𝜋𝑥
𝐿 8𝑚𝐿2 𝜓1 (𝑥) = √ cos
𝐿 𝐿
2 2𝜋 4ℏ2
,𝐿 𝜀2 = 2 2𝜋𝑥
𝐿 8𝑚𝐿2 𝜓2 (𝑥) = √ sin
𝐿 𝐿
3 3𝜋 2𝐿 9ℏ2
, 𝜀3 = 2 3𝜋𝑥
𝐿 3 8𝑚𝐿2 𝜓3 (𝑥) = √ cos
𝐿 𝐿
4 4𝜋 𝐿 16ℏ2
, 𝜀4 = 2 2𝜋𝑥
𝐿 2 8𝑚𝐿2 𝜓4 (𝑥) = √ sin
𝐿 𝐿

A particle in a finite potential box,

the potential energy appears as:

𝐿 𝐿
0 𝑓𝑜𝑟 − ≤ 𝑥 ≤
𝑉(𝑥) = { 2 2
𝑉0 𝑜𝑡ℎ𝑒𝑟𝑤𝑖𝑠𝑒

The Schrodinger equations for different regions are

ℏ2 𝜕 2 𝐿 𝐿
− 𝜓(𝑥) + 𝑉0 𝜓(𝑥) = 𝜀 𝜓(𝑥) 𝑓𝑜𝑟𝑥 < − 𝑎𝑛𝑑 𝑥 >
2𝑚 𝜕𝑥 2 2 2
 𝑑2 2𝑚(𝑉0 − 𝜀)
⟹ 2 𝜓(𝑥) = 𝜓(𝑥)
𝑑𝑥 ℏ2

𝑑2 2𝑚(𝑉0 − 𝜀)
⟹ 𝜓(𝑥) = 𝛽 2 𝜓(𝑥) ; 𝛽=√
𝑑𝑥 2 ℏ2

𝐷2 = −𝛽 2

𝐷 = ±𝛽

𝐷𝜓(𝑥) = ±𝛽𝜓(𝑥)

𝑑
𝜓(𝑥) = ±𝛽𝜓(𝑥)
𝑑𝑥

𝑑𝜓(𝑥)
= ±𝛽 𝑑𝑥
𝜓(𝑥)

𝑑𝜓(𝑥)
∫ = ± ∫ 𝛽 𝑑𝑥
𝜓(𝑥)

ln(𝜓(𝑥)) = ±𝛽 𝑥 + 𝑐

𝜓(𝑥) = 𝐴 𝑒 𝛽𝑥 + 𝐵𝑒 −𝛽𝑥
𝐿
However for region 1 , i.e., 𝑓𝑜𝑟 𝑥 < − 2 , the second term in the wave function becomes infinite
as x→ -∞ , which is physically impossible so unacceptable. Hence
𝐿
𝜓1 (𝑥) = 𝐴 𝑒 𝛽𝑥 𝑓𝑜𝑟 𝑥 < − 2 …(5)

𝐿
Similarly in region 3, i.e., 𝑓𝑜𝑟 𝑥 > 2, the first term becomes infinite as x→ ∞ , which is physically
impossible and unacceptable. Hence
𝐿
𝜓3 (𝑥) = 𝐵 𝑒 −𝛽𝑥 𝑓𝑜𝑟 𝑥 > 2 ……(6)

𝐿 𝐿
In region 2 , i.e., 𝑓𝑜𝑟 − 2 ≤ 𝑥 ≤ 2, ie well region the Schrodinger Eqn appears as :

ℏ2 𝜕 2
− 𝜓(𝑥) = 𝜀 𝜓(𝑥)
2𝑚 𝜕𝑥 2

Which is similar to the equation in infinite potential well. Hence the solution is

𝜓2 (𝑥) = 𝐶 sin 𝑘𝑥 + 𝐷 cos 𝑘𝑥 ….(7)

2𝑚𝜀 ℏ2 𝑘 2
where 𝑘2 = 𝑜𝑟 𝜀=
ℏ2 2𝑚

Now we have to use the boundary condition that the wave function and its first derivative is
continuous across the boundary. While, the continuity of wave function correspond to the
continuity of probability density, the continuity of first derivative of the wave function correspond to
the continuity of current density. So the boundary conditions are:
𝛽𝐿
𝑘𝐿 𝑘𝐿
𝜓1 (𝑥)|𝑥=−𝐿/2 = 𝜓2 (𝑥)|𝑥=−𝐿/2 ⟹ 𝐴 𝑒 − 2 = −𝐶 sin + 𝐷 cos … (7)
2 2

𝑑𝜓1 (𝑥) 𝑑𝜓2 (𝑥) 𝛽𝐿 𝑘𝐿

| = | ⟹ 𝛽 𝐴 𝑒 − 2 = 𝑘𝐶 cos 𝑘𝐿/2 + 𝑘𝐷 sin .. (8)
𝑑𝑥 𝑥=−𝐿/2 𝑑𝑥 𝑥=−𝐿/2 2

𝛽𝐿 𝑘𝐿
𝜓3 (𝑥)|𝑥=𝐿/2 = 𝜓2 (𝑥)|𝑥=𝐿/2 ⟹ 𝐵 𝑒 − 2 = 𝐶 sin 𝑘𝐿/2 + 𝐷 cos . . (9)
2

𝑑𝜓3 (𝑥) 𝑑𝜓2 (𝑥) 𝛽𝐿 𝑘𝐿 𝑘𝐿

| = | ⟹ −𝛽 𝐵 𝑒 − 2 = 𝑘𝐶 cos − 𝑘𝐷 sin . . (10)
𝑑𝑥 𝑥=𝐿/2 𝑑𝑥 𝑥=𝐿/2 2 2

𝛽𝐿
𝑘𝐿
Eqn(9)+ Eqn(7) ⟹ 2 𝐷 cos = (𝐵 + 𝐴) 𝑒 − 2 … … (11)
2

𝛽𝐿
𝑘𝐿
Eqn(9)- Eqn(7) ⟹ 2𝐶 sin = (𝐵 − 𝐴) 𝑒 − 2 … … (12)
2

𝛽𝐿
𝑘𝐿
Eqn(8)- Eqn(10) ⟹2 𝑘𝐷 sin = 𝛽(𝐵 + 𝐴) 𝑒 − 2 … … (13)
2

𝛽𝐿
𝑘𝐿
Eqn(8)+ Eqn(10) ⟹ 2𝑘𝐶 cos = −𝛽(𝐵 − 𝐴) 𝑒 − 2 … … (14)
2

We have two sets of solutions

𝑘𝐿
1) Deviding Eqn(13)/Eqn(11) ⟹ 𝑘 tan = 𝛽 if 𝐵 ≠ −𝐴 𝑎𝑛𝑑 𝐷 ≠ 0 𝑎𝑛𝑑 𝐵 = 𝐴 𝑎𝑛𝑑 𝐶 = 0
2

𝑘𝐿 𝑘𝐿 𝛽𝐿
So energy can be determined from the relation tan 2 = ⟹ 𝜉 tan 𝜉 = 𝜂
2 2

The wave function is 𝜓1 (𝑥) = 𝐴 𝑒 𝛽𝑥 , 𝜓2 (𝑥) = 𝐷 cos 𝑘𝑥 and 𝜓3 (𝑥) = 𝐴 𝑒 −𝛽𝑥

𝑘𝐿
2) Deviding Eqn(14)/Eqn(12) ⟹ 𝑘 cot = −𝛽 if 𝐵 ≠ 𝐴 𝑎𝑛𝑑 𝐶 ≠ 0 𝑎𝑛𝑑 𝐵 = −𝐴 𝑎𝑛𝑑 𝐷 = 0
2

𝑘𝐿 𝑘𝐿 𝛽𝐿
So energy can be determined from the relation cot 2 = ⟹ 𝜉 cot 𝜉 = −𝜂
2 2

The wave function is 𝜓1 (𝑥) = −𝐴 𝑒 𝛽𝑥 , 𝜓2 (𝑥) = 𝐶 sin 𝑘𝑥 and 𝜓3 (𝑥) = 𝐴 𝑒 −𝛽𝑥

𝐿 𝐿 2𝑚𝜀 𝐿 𝐿 2𝑚(𝑉0 −𝜀)

𝜉 = 2𝑘 = 2√ , 𝜂 = 2𝛽 = 2√ ,
ℏ2 ℏ2

𝑚𝑉0 𝐿2 𝑚𝑉0 𝐿2
𝜉 2 + 𝜂2 = 2ℏ2
equation of a circle with radius 𝑟 = √ 2ℏ2
 The energy can be determined by numerical computation of the relation s

𝜉 tan 𝜉 = 𝜂 and 𝜉 cot 𝜉 = −𝜂

Or from graphical solution from intersection of the curves 𝜉 tan 𝜉 = 𝜂 and 𝜉 cot 𝜉 = −𝜂 with the
𝑚𝑉0𝐿2
circle of radius 𝑟 = √ 2ℏ2

Number of bound states: If the radius of circle which depends on 𝑉0 𝑎𝑛𝑑 𝐿 remain between
𝑛𝜋 (𝑛+1)𝜋
𝑎𝑛𝑑 , then there will be (n+1) bound states. To find the number of bound states we need
2 2
to calculate radius r as given above.

Potential
well

Confin
ed
envelo

AlGa Ga AlGa
As As As
 Formation of a quantum well, the width of well should be in the order of deabroglie wavelength of
the material to achieve quantum confinement effect.