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APPLICATION: PARTICLE IN A BOX (Qualitative analysis)

If a particle is confined into a rectangular volume, the


same kind of process as in 1D box , can be applied to a three-
dimensional "particle in a box", and the same kind of energy
contribution is made from each dimension. The energies for a
three-dimensional box are

The 3D steady-state form of Schrodinger’s equation for the


particle within the box may be written as

 2 2  2   2m
 2  2  2   2 E ( x, y, z )  0...............................(1)
 x y z  
After solving and putting boundary condition similar to 1D box we get following energy eigen
values

 2 2  2
E n  
nx n y nz  2 2 ..................................(2)
 8mL2 
 

where 
2

n2 n  n  n
2 2
x y z

WAVE FUNCTIONS

The wave function of a particle in 3D box whose energy is E are obtained in similar fashion as
in 1D box and are
 2
3/ 2
 n   n y   n 
n    sin x x . sin y . sin z z ....................(3)
x n y nz
L   L  L  L 

This gives a more physically realistic expression for the available energies and wave functions
for contained particles. This expression is used in determining the density of possible energy
states for electrons in solids.
Degeneracy or Degenerate states:

Consider the following set of values of quantum numbers


 nx  1   nx  2   nx  2 
   
 n y  2 .. n y  1 .. n y  2 ...............(1)
   
 z
n  2  z n  2  z n  1 
We get following energy eigen value

 9  2 2
En   2 
  ..................................(2)
 8mL 

where 
9 1 2 2
2 2 2

This means that for three different sets of quantum numbers we get same eigen values of energy.

But we get three different eigen functions as

 1   2   2 
 1, 2, 2  A sin x . sin y . sin z ....................(3a)
 L  L  L 

 2   1   2 
 2,1, 2  A sin x . sin y . sin z ....................(3b)
 L  L  L 

 2   2   1 
 2, 2,1  A sin x . sin y . sin z ....................(3c)
 L  L  L 

Thus for the same energy eigen value there corresponds three different eigen
functions. Such functions are called degenerate functions and this is termed as
3- fold degeneracy.
This concept is used to explain the splitting on spectral lines in atom i.e. fine structure of spectral
lines.

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