Particle in a Three Dimensional Box

Let us consider a particle enclosed in a three dimensional box of length a, breadth b and

height c. The walls are rigid and hard. The potential energy is assumed to be zero inside

the box. As no force acts on the particle inside the box, therefore in this region

c Y

b
0 a X

Figure A-1 Particle in a three dimensional box

0<x<a

0<y<b

0<z<c

the potential energy V (x, y, z) = 0 and for region outside the box, V (x, y, z) = 

The Schrödinger equation for this case is

2m
 2  ( E  V )  0
2

with

2   h

For a particle inside the box, V = 0 , the equation is

1
  2mE 
 2   2   0 (A1)
  

 2  2  2 2mE
or     0 (A2)
x 2
y 2
z 2
2

Applying the method of separation of variables, we get

 ( x, y, z)  X ( x) Y ( y) Z ( z) (A3)

This means wave function  (x, y, z) is equal to the product of the functions X, Y and Z.

Taking the second derivatives of  (x, y, z) and substituting their values in Eqn. A2, and

dividing by XYZ, we get

 1  d X  1  d Y  1  d Z  2mE 
2 2 2
  2   2   2   2   0 (A4)
 X  dx  Y  dy  Z  dz   

2mE
For a particular value of kinetic energy the term has a constant value. As velocity is
2

a vector quantity and can be resolved into three components along the co-ordinate axes,

therefore kinetic energy E can be resolved into three components such that

E  Ex  E y  Ez (A5)

Substituting this value in Eqn. A4, it becomes

2
  1  d 2 X 2mEx   1  d 2Y 2mE y   1  d 2 Z 2mEz 
  2  2     2       2 0
 X  dx    Y  dy  2   Z  dz 2  

Here first term is a function of x only and second term of y only and the third is a function

of z only. And the RHS = 0. This is possible only if each term is equal to zero. i.e.,

d2X  2mE 
  2 x X  0
  
2
dx
2
d Y  2mE y 
2
  2 Y  0 (A6)
dy   
d 2Z  2mE 
  2 z Z  0
dz2
  

Let us consider now the first equation,

d2X  2mE 
  2 x X  0
  
2
dx

The solution is of the form

X = Ax sinkx x + Bx coskx x (A7)

When x = 0, X = 0, and hence Bx = 0

and when x = a, X = 0 = Ax sinkx a

n x
Hence kx a = nx  ; or k x  . Eqn. (A7) becomes
a

n x
X = Ax sinkx x. This is possible when k x 
a

n x x
Thus X  Ax sin
a

2
Using normalization principle, we can prove Ax 
a

3
  2  n x x
and so X    sin
 a  a

Similarly

 2 n y y  2 nz
Y    sin and Z    sin z
 b  b  c  c

Thus the wave function,

 n x , n y , nz  X ( x ) Y ( y ) Z ( z )

i.e.,

 8  n x x n y y nz
 ( x, y, z )    sin sin sin z (A8)
 abc  a b c

If it is a cube, then

 8  nx n y y nz
 ( x, y, z )   3 
sin x sin sin z (A9)
 a  a a a

This is eigen values of the wave function. Let us now discuss the eigen values of energy.

E = Ex + Ey + Ez

Refer Eqn. 1.58

h 2 k x2 n x2 2
Ex  with k x2 
8 2 m a2

i.e.,

h2 n x2 2 h 2 n x2
Ex  
8 2 m a2 8m a 2

and

4
 h 2 n 2y
Ey 
8m b 2

and

h 2 n z2
Ez 
8m c 2

So

h2  nx n y nz 
2 2

2
E nx , n y ,nz  E x  E y  E z   2   2
8m 2 
 a b 2
c 


For a cubical box

h2 n2h2
E (n x , n y , n z )  (n x2  n 2y  n z2 )  (A10)
8m a 2 8m a 2

where n 2  nx2  n 2y  nz2

i.e., n2 is the sum of the squares of three integers in a three dimensional case.

Conclusions

In a cubical box the energy depends on the sum of the squares of the quantum numbers.

Consequently the particle having the same energy in an excited state will have different

energy states or wave functions due to the different combinations of the same set of

quantum numbers. Such states or energy levels are said to be degenerate energy states.

The following column gives the first degenerate energy state.

nx ny nz

5
 2 1 1

1 2 1

1 1 2

It is now understood that there are different eigen functions and hence three different

energy states for free electrons to occupy. Each state has the same energy of magnitude

6h 2
. Therefore this energy state is called triply degenerate or three-fold degenerate.
8ma 2

Now have a look on the following table.

Table A1 Different energy states for particles in a cubical box and the corresponding
energy levels

Energy levels and Quantum numbers Degree of Degeneracy

energy values
h2 Non-degenerate
3 2 (1, 1, 1)
8ma energy state
h2 Three fold degenerate
6 2 (2, 1, 1), (1, 2, 1), (1, 1, 2)
8ma energy state
h2 Three fold degenerate
9 (2, 2, 1), (1, 2, 2), (2, 1, 2)
8ma 2 energy state
h2 Three fold degenerate
11 2 (1, 1, 3), (3, 1, 1), (1, 3, 1)
8ma energy state
h2 Second non-
12 2
8ma (2, 2, 2) degenerate energy
state
h2 (1, 2, 3), (3, 1, 2), (2, 3, 1) Six fold degenerate
14 2
8ma (1, 3, 2), (2, 1, 3), (3, 2, 1) energy state