Module 3 – Elementary Quantum Mechanics

(Particle in a Box)
 Particle in a Box
In quantum mechanics, the particle in a box model
describes a particle free to move in a small space
surrounded by impenetrable barriers
The model is mainly used as a hypothetical example
to illustrate the differences between classical and
quantum systems

In classical mechanics, a ball trapped inside a large box moves in a straight line
with the same speed until it is reflected from the walls
But when the box becomes very narrow (in nanometer scale), the quantum
effects become important
The particle may only occupy certain positive energy levels and also the particles
cannot have zero energy
 Application of Schrödinger Wave Equation to a
Particle (Electron) enclosed in a One-dimensional Box

A particle in a box problem is a common application

of a quantum mechanical model to a simplified

system consisting of a particle moving horizontally

within an infinitely deep well from which it can not

escape

The solutions to the problem give

possible values of energy (En) & wave function [ψ (x)] that the particle can possess

│ψn│2 - Probability of locating the particle at a certain position within the box at a

given energy level

 Application of Schrödinger Wave Equation to a
Particle (Electron) enclosed in a One-dimensional Box

To solve the problem for a particle in a one-dimensional box, we must

follow four steps

1. Define the Potential Energy (V)

2. Solve the Schrödinger Equation

3. Define the Wave function

4. Define the allowed energies

 Particle in a Box (Step 1 – Define Potential Energy)

Consider a particle (electron) of mass ‘m’ moving in a

one-dimensional box of width ‘L’ and infinite height

Assume that the particle is freely moving inside the box

Movement of the particle is restricted by the walls of

the box

Particle is confined between the length ‘L’ of the box and has elastic collisions with the

walls

For a particle moving freely at the bottom of the potential box, the potential energy is

very low (Potential energy is assumed to be zero (V = 0) between x = 0 and x = L)

 Particle in a Box (Step 1 – Define Potential Energy)

Potential energy of the particle at the walls is infinite

The particle cannot escape from the box due to infinite

potential energy outside the potential well (V = ∞)

V = 0 for 0  x  L
V =  for 0  x  L

Since the particle cannot be present outside the box, its probability function is zero

 = 0 for 0  x  L
2

Since the particle is present inside the box, the probability function is not equal to zero

  0 for 0  x  L
2
 Particle in a Box (Step 2 – To Solve Schrödinger Equation)

Schrödinger's 1-D time independent equation is

d 2 2m
2
+ 2 (E − V ) ψ = 0
dx 

Inside the box, the particle has only kinetic

energy and potential energy V = 0

d 2 2m 2m
= 2
+ 2 Eψ=0 Let E K
dx 2
 2

d 2
2
+ K 2
ψ=0 (This equation is a second order differential equation)
dx
The general solution of this equation consists
of two arbitrary constants A and B
ψ ( x) = A sin Kx + B cos Kx
Particle in a Box (Step 2 – To Solve Schrödinger Equation)
(Values of A and B can be found out using
ψ ( x) = A sin Kx + B cos Kx
boundary conditions)

Boundary Condition at x= 0
When x = 0 ψ = 0 (There is no probability to find the particle at x = 0)
ψ ( x) = A sin Kx + B cos Kx

0 = A sin 0 + B cos 0 sin 0 = 0 & cos 0 = 1

B=0 (since cos 0 = 1)

Boundary Condition at x = L

When x = L ψ = 0 Since B = 0
0 = A sin KL + B cos KL A sin KL = 0
Step 2 - To Solve Schrödinger Step 3 – Define Wave Function
Equation

Boundary Condition at x=L→ψ=0 ψ ( x) = A sin Kx + B cos Kx

0 = A sin KL + B cos KL
n
A0 B=0 K=
Since B = 0 → A sin KL = 0 L

A  0, since already B = 0 n
ψ ( x) = A sin x
L
sin KL = 0 sin n = 0
KL = n
n
n Wave function ψ ( x) = A sin x
K= , n = 1, 2, 3, . . . . . . L
L
 Particle in a Box (Step 4 – Define Allowed Energies)
Initially we assumed 8 2 m n 2 2
2
E=
h L2
2m  h h 2

E=K 
2  = →  2
= n2
4 2 
2
8m
 2  2
E= 2
h L
2m n2
K =
2
E 8 m
2 8m
En = 2
 h 
2 K2 = E 2
h 2 h L
 4 2 
 
n 2h2
En =
8 2
m 8mL2
K2 = 2
E
h
Energy of the particle
n n 2 2 n h 2 2
K= K = En =
2
L L2
8mL2
 Energy of a Particle in a Box of length L

n2 h2 h h = ħ2π
En = ħ=
8mL2 2π

n2 (ħ2π)2 n2 ħ2 4π2 n2 ħ2 π2
En = En = En =
8mL2 8mL2 2mL2

n2 h2 n2 ħ2 π2
En = En =
8mL2 2mL2
 Calculation of Energy Levels
n 2h2
The energy values of the particle depends upon the ‘n’ values E n =
8mL2
h2
For n = 1 → E1 = En = n2 E1
8mL2

4h 2
For n = 2 → E 2 = 2
= 4 E1 Energy levels are found to be discrete
8mL (specific values)

In classical mechanics, the energy levels

2
9h are continuous
For n = 3 → E 3 = 2
= 9 E1
8mL
(n = quantum number)

16h 2
For n = 4 → E 4 = 2
= 16E1
8mL
Energy Level Diagram
 n𝜋
ψ (𝑥) = A sin 𝑥
L

For n = 1
At 𝑥 = 0, ψ = 0
At 𝑥 = L, ψ = A sin π

For n = 2
At 𝑥 = 0, ψ = 0
At 𝑥 = L, ψ = A sin 2π
2π
0 π 3π

2π
For n = 3 0 π
At 𝑥 = 0, ψ = 0
At 𝑥 = L, ψ = A sin 3π
0 π
For n = 1, the probability of finding the particle is maximum in the
middle of the box
For n = 2, the probability is minimum in the middle of the box
 n
ψ ( x) = A sin x
L

L
For n = 1, the probability is maximum at 𝑥 =
2
L 3L
For n = 2, the probability is maximum at 𝑥 = &
4 4
L
For n = 2, the probability is minimum at 𝑥 =
2
L 2L
For n = 3, the probability is minimum at 𝑥 = &
3 3
 n
ψ ( x) = A sin x for 0 < 𝑥 < L and n = 1, 2, 3,
L
Actual probabilities can be computed only after ψn is normalized

We must be sure that all probabilities sum to unity ( Probability = 1)

L L
L nπ 2 𝑛π𝑥
∞
2 𝑑𝑥 = න 𝐴 sin 𝑥 𝑑𝑥 = A2 න sin2 𝑑𝑥
න ψ𝑛 2 𝑑𝑥 = න ψ 0 L 0 L
−∞ 0

2
1
sin θ = 1 − cos 2θ
2
L 1 L
2𝑛π𝑥 A2 L L 2𝑛π𝑥
න ψ 2 2
𝑑𝑥 = A න 1 − cos 𝑑𝑥 = 2
‫׬‬0 𝑑𝑥 − ‫׬‬0 cos
L
𝑑𝑥
0 0 2 L

∞ A2 L 2𝑛π𝑥 𝐿 L
න ψ𝑛 2 𝑑𝑥 = 𝑥− sin = A2
2 2𝑛π L 0
2
−∞
 ∞
L
න ψ𝑛 2 𝑑𝑥 = A2
−∞ 2

To normalize ψ we must assign a value to lψnl2 dx is equal to the

probability P dx of finding the particle between x and x + dx, rather than
merely proportional to P dx

lψnl2 dx is equal to P dx, then it must be true that

∞
න ψ𝑛 2 𝑑𝑥 = 1
−∞ The normalized wave
functions of the particle are
L
A2 =1
2
2 𝑛π𝑥
ψn = sin
𝐿 𝐿
2
A=
𝐿
 Important Facts from Particle in a Box

1. The energy of a particle is quantized. This means it can only take on discrete
energy values

2. The lowest possible energy for a particle is NOT zero (even at 0 K).
This means the particle always has some kinetic energy

3. The square of the wave function is related to the probability of finding the particle
in a specific position for a given energy level

4. The probability changes with increasing energy of the particle and

depends on the position in the box you are attempting to define the energy

5. In classical physics, the probability of finding the particle is independent of the

energy and the same at all points in the box