Applications of Schrödinger's

wave equation
Reference:
Book 1(theory): Concept of Modern Physics
by “A. Beiser”
Book 2(practice): Problems and solutions in Solid state
Physics by “S.O.Pillai
Schrödinger's wave equation

2m
 2  2
( E  V )  0

 2
 
   V   i
2

 2m  t

 i * i   1

 i * j   0 and  j * i   0
 Operator

2
Energy   V
2
i
2m t

Momentum p 
i

Velocity Operator v  
im

Potential Energy operator V

Position operator r

O   Value 
Expectation Values of Variables

 f   * f 

 r   * r

 p   * 
i

 2

 E   *     V 
2

 2m 
 Applications of Schrodinger Wave
Equations
• Particle in one dimensional box
• Particle in three dimensional box
• Potential Barrier
• Harmonic Oscillators
 Particle in one dimensional box
• Let a single particle, e.g. a
gas molecule of mass m is V=0
confined within a box of V=
V=
length L.
• The particle can move freely
within region 0<x<L. Inside
the box. X=0 X=L

• The potential V inside the box is zero

• At x=0 and x=L the potential rises suddenly to a
very large value
• Outside the boundary the potential is very large
This is problem of single dimension box
• Particle is bounded to a box
• The Schrodinger wave equation for the particle can
be written as
2m
 2  2
E  0

One dimensional case x direction

2 2mE
   0
x 2 2

Let put
2mE
2
 k 2

 2
 k 2
 0
x 2

The solution of this differential equation is of type

 ( x)  A sin kx  B cos kx
Where A , B are constants
  ( x)  A sin kx  B cos kx
Since the particle cannot have infinite energy
So particle cannot exist outside the box Classical view
So  is zero outside and on the boundary of box
Apply boundary condition
  0, when x=0
B0
Apply second boundary condition
  0, when x=L
A sin kL  0
kL  n
A sin kL  0
n Where
k
L n  1, 2,3, 4.....
  ( x)  A sin kx  B cos kx
So solution can be written as
n x
 ( x)  A sin
L
Also
n 2mE
k and 2
 k2
L
So
2mE n 2 2
2
 2
L

n 2 2 2
E
2mL2
Where
n  1, 2,3, 4.....
Quantization of energy
 n x
 ( x)  A sin
L

Normalized
2 n x
 ( x)  sin
L L
1. Calculate the energy difference between the ground state
and the first excited state for an electron in one dimensional
rigid box of length 10 A.

n 2 2 2
E
2mL2
For ground state n=1 and first excited state n=2

4 2 2  2 2 3 2 2
E  Eexcited - Eground  2
 2

2mL 2mL 2mL2

3 2 2
E  2
 113.1eV
2mL
2. Can you observe energy state of ball of mass 10g moving in a
box of length 10 cm.

n 2 2 2
E
2mL2

E  n2 3.4 1045 eV
E1  3.4 1045 eV
E2  13.6 1045 eV
E3  30.6 1045 eV

So they are very close to each other, so not separated

 Operator to calculate Energy of
particle in box
2
Energy  2  V
2m
2 n x V 0
 ( x)  sin
L L
2
 2 n x 
H  E      E
2
sin
2m  L L 
2
2  2 n x 
 2 
 sin   E n2 2
2
2 n x 
2m x  L L   sin   E
2m L2 L L 

n
2 2 2 n 2 2 2
  E E
2m L2 2mL2
Expectation Values of Variables to
calculate expected value of Energy
 f   * f 

 p   * 
i

 2

 E   *     V 
2

 2m 

2 n x
 ( x)  sin
L L
  2

 E   *    2  V 
 2m 

2 n x
 ( x)  sin
L L
n x   2 n x
L 2
2
 E   sin    2
 V  sin x
L L  2m  L L
0
V 0

n x  2 n x
L
2 2
 Ex   
2mL 0
sin
L x 2
sin
L
x

n2 2 2 n x
2 L

2 
 Ex  sin x
mL L 0 L
 n x 
1  cos 2
n 
2 2 2 L
L  x
mL L2 0 
 Ex   
2 
 
  n x 
1  cos 2
n 
2 2 2 L

2 
 Ex  L
 x
mL L 0  2 
 

2n x
L

sin
2
n
2 2
L
 Ex  L 
2mL L2 2n
L 0

n2 2
2

2 
 Ex  L  0  0  0
2mL L

n 2 2 2
 Ex 
2mL2
n 2 2 2
E
2mL2
Extension to 3 dimensional box

A three dimensional case

Now consider a particle of mass m and total energy E is
confined in three dimensional box of x dimension length Lx, y
direction Ly and z direction length Lz.

The particle moves freely within these lengths, as potential is

zero inside the box

This box is bounded by a large potential barrier

The particle is confined in 3 dimensional box, and restricted to

outside by a very large potential barriers
The Schrodinger wave equation inside the box
2m
 2  2
E  0

2 2 2 2mE
  2  2  2   0
x 2
y z

Let put
2mE
2
 k 2

 2  2  2
   k 2
 0
x 2
y 2
z 2

Lets use separation of variables

  X ( x)Y ( y)Z ( z)
Total wave function

nx 2 2 2 ny  nz 2 2 2
2 2 2

E  Ex  E y  Ez  2
 2

2mLx 2mLy 2mLz 2
2
 2  nx 2
nz 2 
ny 2
E  2  2  2 
2m  Lx Ly Lz 

h 2  nx 2 ny nz 2 
2

E  2  2  2 
8m  Lx Ly Lz 