The Schrodinger Equation

The Schrodinger Equation

  x, y, z, t  2
i  2   x, y, z, t   V  x, y, z, t    x, y, z, t 
t 2m

Where i  1 , m denotes the mass of the particle, and V  x, y, z, t  represents the

potential energy of the particle (the potential for short).

2 2 2
2   
x 2 y 2 z 2

The Time – Independent Schrodinger Equation

We will discuss situations in which the potential energy of a non – relativistic

massive particle, does not have any explicitly dependence on time. i.e.,

V  x, y, z, t   V  x, y, z 

In these kinds of situations we can use separation of variables, and write,

  x, y, z, t     x, y, z   T  t 

Where T  t  represents the part of the wave function that depends on time, and

  x, y, z  represents the part of the wave function that depends on the spatial

coordinates.
iE
 t
T t   e
   x, y, z, t     x, y, z 
2 2

Conclusion: Whenever the potential energy of a non – relativistic

massive particle, does not have any explicitly dependence on time

( V  x, y, z, t   V  x, y, z  ), the wave function of the particle takes the form,

iE
 t
  x, y, z, t     x, y, z  e , which evolves with time, but the probability density

Function takes the form,   x, y, z, t     x, y, z  , which means it does not

2 2

evolves with time (i.e. the probability density function is stationary).

The time independent Schrodinger equation,

2m
2  x, y, z   2
 E  V  x, y, z   x, y, z   0

The properties of the solution to Schrodinger time independent equation

  x, y, z  must be a “well – behaved” function. In other words,   x, y, z  must be

finite everywhere, must have a one to one correspondence everywhere, and must

be continuous everywhere.

In addition we have a physical condition for   x, y, z  , that it must be

normalizable (so that we will be able to interpate   x, y, z  as a probability
2

density function),

   x, y, z 
2
dV  C
V

Where C denotes a constant.

The normalization condition for   x, y, z  ,

    x, y, z 
2
dV  1
V

For   x, y, z  to be normalaizable means that   x, y, z  must be continuous

  x, y, z   0 
everywhere and vanish at the edges   , and its first
 x   or y   or z   
derivative    x, y, z  (with respect to a spatial coordinate) must be continuous

everywhere except at points in which the potential energy goes to infinity, and

   x, y, z   0 
vanish at the edges  .
 x   or y   or z   
One Dimensional and Infinite Potential Well

 

x0 xL

, x  0

V  x   0, 0  x  L
, x  L


The time independent Schrodinger equation in the one dimensional case,

d 2  x  2m
 2  E  V  x    x   0
dx 2

Let us divide space into three regions: x  0, 0  x  L, x  L .

  

I II III

x0 xL

 I  x    III  x   0

2  n 
 II  x   sin  x
L  L 

2mE
k 2

2
Where k is the wave number ( k  ).


2 2
En  n2 , n  1, 2,3,...
2mL2
  II  x   II  x 
2

For n  1 the probablilty denstiy fucntion looks like this,

 II  x 
2

x0 xL

In words, the probability density function becomes uniform, i.e. we return to

classical mechanics.
The energy levels diagram,

2 2
n4 E4  16
2mL2

2 2
n3 E3  9
2mL2

2 2
n2 E2  4
2mL2

2 2
n 1 E1 
2mL2

2 2
Note that the energy of the ground state is, E1   0.
2mL2
One Dimensional Potential Step

E  V0  0

m V0

x0

0, x  0
V  x  
V0 , x  0

According to classical mechanics, the particle will cross the point x  0 (because

its energy is larger than V0 ) and will continue to move to the right (all the way to

x   ). In other words, we expect a full transmission of the particle and zero

reflection.

The time independent Schrodinger equation in the one dimensional case,

d 2  x  2m
 2  E  V  x    x   0
dx 2

Let us divide space into two regions: x  0, x  0 .

 E  V0  0

m V0

I II

x0

For region I ( x  0 ),

d 2 I  x  2m
 2  E  0 I  x   0 
dx 2

d 2 I  x  2mE
 2  I  x  0
dx 2

Let us define a real and positive constant,

2mE
k1  2

Now we can write down the equation in the following way,

d 2 I  x 
2
 k12 I  x   0
dx

The general solution of an equation of this form is,

 I  x   Aeik x  Beik x
1 1

Where A, B represent constants that we must find by using the continuity

conditions and the normalization condition.

Aeik1x represents a particle moving from left to right.

Beik1x represents a particle moving from right to left.

For region II ( x  0 ),

d 2 II  x  2m
 2  E  V0  II  x   0 
dx 2

d 2 II  x  2m  E  V0 
  II  x   0
dx 2 2

Let us define another real and positive constant,

2m  E  V0 
k2  2

Now we can write down the equation in the following way,

d 2 II  x 
2
 k22 II  x   0
dx

The general solution of an equation of this form is,

 II  x   Ceik x  Deik x
2 2

Where C, D represent constants that we must find by using the continuity

conditions and the normalization condition.

Ceik2 x represents a particle moving from left to right.

Deik2 x represents a particle moving from right to left.

Since there is now way for the particle to move from right to left while it is found

in region II , we conclude that, D  0 .

Hence, the form of the wave function at region II ,

 II  x   Ceik x 2
Let us define the transmission and reflection coefficients.

The reflection coefficient,

2
B
R 2
A

The transmission coefficient,

2
C k2
T 2

A k1

The following relation must always hold,

R T 1

According to classical mechanics, we expect,

R  0, T  1

We will check what actually happens according to quantum mechanics.

Let us use the continuity conditions,

 I  x  0   II  x  0

 I  x  II  x 

dx x 0
dx x 0

 I  x  0   II  x  0  Aeik 0  Beik 0  Ceik 0 

1 1 2

Ae0  Be0  Ce0  A 1  B 1  C 1 

A B  C
  I  x  II  x 
  ik1 Aeik1 0  ik1Beik1 0  ik2Ceik2 0 
dx x 0
dx x 0

ik1 Ae0  ik1Be0  ik2Ce0  ik1 A 1  ik1B 1  ik2C 1  ik1 A  ik1B  ik2C 

k1 A  k1B  k2C

Let us plug C  A  B in the equation we got from the continuity condition on the

first derivative of the wave function,

k1 A  k1B  k2C  k1 A  k1B  k2  A  B   k1 A  k1B  k2 A  k2 B 

k1 A  k2 A  k1B  k2 B  A  k1  k2   B  k1  k2  

B k1  k2

A k1  k2

2 2
 B  k k 
2 2
B B
    1 2  
 A   k1  k2 
2
A A

2
 k k 
R 1 2  0
 k1  k2 

Because k1  k2 .

A B  C 

BCA

Let us plug B  C  A in the equation we got from the continuity condition on the

first derivative of the wave function,

k1 A  k1B  k2C  k1 A  k1 C  A  k2C  k1 A  k1C  k1 A  k2C 

2k1 A  k1C  k2C  2k1 A  C  k1  k2  

C 2k1

A k1  k2
 2 2
 C   2k1 
2 2
C C
    
 A   k1  k2 
2
A A

2 2
k  2k1  k2
C
T  2  2    1
A k1  k1  k2  k1

Let us check our results,

 k  k   2k1  k2  k1  k2 
2 2 2
4k12 k
R T   1 2        2
 k1  k2   k1  k2  k1  k1  k2   k1  k2  k1
2 2

k12  2k1k2  k22 4k1k2 k12  2k1k2  k22  4k1k2 k12  2k1k2  k22
R T     
 k1  k2   k1  k2   k1  k2   k1  k2 
2 2 2 2

k  k 
2

R T  1 2 2 1
 k1  k2 

R T 1
 V0
m 0  E  V0

x0

0, x  0
V  x  
V0 , x  0

According to classical mechanics, the particle will never be able to cross the point

x  0 (because its energy is smaller than V0 ). In other words, we expect a full

reflection of the particle and zero transmission.

m V0
0  E  V0

I II

x0

The time independent Schrodinger equation in the one dimensional case,

d 2  x  2m
 2  E  V  x    x   0
dx 2

Let us divide space into two regions: x  0, x  0 .

For region I ( x  0 ),

d 2 I  x  2m
 2  E  0 I  x   0 
dx 2

d 2 I  x  2mE
 2  I  x  0
dx 2

Let us define a real and positive constant,

2mE
k1  2

Now we can write down the equation in the following way,

d 2 I  x 
2
 k12 I  x   0
dx
The general solution of an equation of this form is,

 I  x   Aeik x  Beik x
1 1

Where A, B represent constants that we must find by using the continuity

conditions and the normalization condition.

Aeik1x represents a particle moving from left to right.

Beik1x represents a particle moving from right to left.

For region II ( x  0 ),

d 2 I  x  2m d 2 II  x  2m  E  V0 
2  0 I  
 E  V  x  0    II  x   0 
dx 2 dx 2 2

d 2 II  x  2m V0  E 
  II  x   0 
dx 2 2

Let us define a real and positive constant,

2m V0  E 
k2  2

Now we can write down the equation in the following way,

d 2 II  x 
2
 k22 II  x   0
dx

The general solution of an equation of this form is,

 II  x   Cek x  De k x
2 2

Where C, D represent constants that we must find by using the continuity

conditions and the normalization condition.

The normalization condition implies that the wave function must go to zero when

x   .
At the edge of region II ( x  0 ), we get x   .

De k2 x  0
x 

Cek2 x  
x 

Hence, we must demand, C  0 .

Thus we see that in region II ( x  0 ), the wave function is,

 II  x   De k x 2

Let us use the continuity conditions,

 I  x  0   II  x  0

 I  x  II  x 

dx x 0
dx x 0

 I  x  0   II  x  0  Aeik 0  Beik 0  De k 0 

1 1 2

A B  D

 I  x  II  x 
 
dx x 0
dx x 0

ik1 Aeik10  ik1Beik1 0  k2 De k2 0 

ik1 A  ik1B  k2 D

Let us plug A  B  D in the equation we got from the continuity condition on the

first derivative of the wave function,

ik1 A  ik1B  k2 D  ik1 A  ik1B  k2  A  B   ik1 A  ik1B  k2 A  k2 B 

 ik1 A  k2 A  ik1B  k2 B  A  ik1  k2   B ik1  k2  

B ik1  k2

A ik1  k2

2 *
 B  B  ik  k  ik  k ik1  k2 ik1  k2
2 *
B B
     1 2   1 2   
 A  A  ik1  k2  ik1  k2 ik1  k2 ik1  k2
2
A A

i 2 k12  ik1k2  ik1k2  k22   1  k1  k2 k12  k22

2 2 2
B
 2 2   1
A
2
i k1  ik1k2  ik1k2  k22   1  k12  k22 k12  k22

R 1

  x

x0

  x
2
One Dimensional Finite Potential Barrier

V0
m E

I II III

x0 xL

0, x0

V  x   V0 , 0  x  L
0, xL


The continuity conditions,

 I  x  0   II  x  0

 II  x  L    III  x  L 

 I  x  II  x 

dx x 0
dx x 0

 II  x   III  x 

dx xL
dx xL
One Dimensional Harmonic Oscillator

The force,

F  kx

The potential energy,

1 2
V  x  kx
2

The solution according to classical mechanics (Newton’s laws describe the

dynamics),

F  ma  kx  mx 

k
x x0
m

We define the angular frequency,

k

m

and write the equation of motion in the following way,

x  2 x  0

The general solution,

x  t   A cos t   B sin t 

 V  x

Etot

x
xmin xmax

According to classical mechanics the particle can move in the region, xmin  x  xmax .
Now let us see what happens when we use quantum mechanics for this problem

(use the Schrodinger equation to describe the dynamics).

The potential energy,

1 2
V  x  kx
2

We define the angular frequency,

k

m

k k
  2  
m m

k  m 2

Thus, we can write the potential energy in the following way,

1 1
V  x   kx 2  m 2 x 2 
2 2

1
V  x  m 2 x 2
2

The time independent Schrodinger equation in the one dimensional case,

d 2  x  2m
 2  E  V  x    x   0
dx 2

In this case we obtain,

d 2  x  2m  1 
 2  E  m 2 x 2   x   0
 
2
dx 2

Let us define,
2E
 

 
E 
2

m
y x

x y
m

x2  y2
m

m dy m
y x   dx  dy 
dx m

dx 2  dy 2
m

Let us plug these relations into Schrodinger time independent equation,

d 2  x  2m  1 
 2  E  m 2 x 2   x   0 
 
2
dx 2

d 2  y  2m   1 
 2 
  m 2  y 2   y   0 
dy 2  2 2 m 
m

d 2  y  m 2m    2
  2   y   y   0 
 2 
2
dy 2

d 2  y  m 2m 
2
  2    y 2   y   0 
dy 2

d 2  y  m m
2
    y 2   y   0 
dy

d 2  y 
   y 2   y   0
dy 2
This is the “equation of motion” for a simple harmonic oscillator in quantum

mechanics.

If one solves this equation he obtains the following,

 1
En   n    , n  0,1, 2,3,...
 2

The energy of the ground state of a simple harmonic oscillator is,

1
E0    0, n0
2

The wave function,

1
 m  4 n  2
1 y2

  2 n ! H n  y  e

 n  y   2

 

Where H n  y  denotes Hermit’s polynomials.

For example,

H0  y   1
H1  y   2 y
H2  y   4 y2  2

The wave function of a simple harmonic oscillator, at the ground state,

1
m 2
 m  4 
 0  y  
x
 e
2

 
A Three Dimensional Potential

We will discuss situations in which the potential energy of a non – relativistic

massive particle, does not have any explicitly dependence on time. i.e.,

V  x, y, z, t   V  x, y, z 

In these kinds of situations we can use separation of variables, and write,

  x, y, z, t     x, y, z   T  t 

Where T  t  represents the part of the wave function that depends on time, and

  x, y, z  represents the part of the wave function that depends on the spatial

coordinates.
iE
 t
T t   e

If in addition to the fact that the potential energy has no explicit dependence on
time, we can also break in the following way,

V  x, y, z   V1  x   V2  y   V3  z 

Then we can perform an additional separation of variables,

  x, y, z    1  x   2  y   3  z 

The time independent Schrodinger equation in the three dimensional case,

2m
2  x, y, z   2
 E  V  x, y, z   x, y, z   0

Let us plug the separation of variables into Schrodinger time independent

equation,

 2 2 2  2m
2  1 
 2    x  2  y   3  z   2  E  V  x, y, z  1  x   2  y   3  z   0 
 x y z 
2
 d 2 1  x  d 2 2  y  d 2 3  z 
 2  y   3  z    1  x   3  z    1  x   2  y   
dx 2 dy 2 dz 2
2m
 2  E  V  x, y, z   1  x   2  y   3  z   0

Let us divide by  1  x   2  y   3  z  ,

1 d 2 1  x  1 d 2 2  y  1 d 2 3  z  2m
      2  E  V  x, y, z    0
1  x dx 2  2  y dy 2 3  z dz 2

Now let us our assumption that,

V  x, y, z   V1  x   V2  y   V3  z 

1 d 2 1  x  1 d 2 2  y  1 d 2 3  z  2m
      2  E  V1  x   V2  y   V3  z   0
1  x dx 2  2  y dy 2 3 z dz 2

Let us write the total energy of the particle in the following way,

E  E1  E2  E3

When we plug it into the equation we got we get,

1 d 2 1  x  1 d 2 2  y  1 d 2 3  z 
    
1  x dx 2  2  y dy 2 3  z dz 2
2m
 2
 E1  E2  E3  V1  x   V2  y   V3  z    0 

1 d 2 1  x  2m 1 d 2 2  y  2m 1 d 2 3  z 
   E
2  1
 V1  
x      E
2  2
 V2  
y   
1  x dx 2  2  y dy 2 3 z dz 2
2m
 2
 E3  V3  z    0
Now we can define 3 functions,

1 d 2 1  x  2m
f  x    2  E1  V1  x  
1  x dx 2

1 d 2 2  y  2m
g  y    2  E2  V2  y  
 2  y dy 2

1 d 2 3  z  2m
h z    2  E3  V3  z  
3  z dz 2

Then we can write the equation in the following way,

f  x  g  y  h  z   0

The simplest solution for this equation is,

f  x  g  y  h  z   0

From this conclusion we obtain three one dimensional equations that we need to

solve,

d 2 1  x  2m
 2  E1  V1  x   1  x   0
dx 2

d 2 2  y  2m
 2  E2  V2  y   2  y   0
dy 2

d 2 3  z  2m
 2  E3  V3  z   3  z   0
dz 2

Conclusion: whenever V  x, y, z, t   V1  x   V2  y   V3  z  , we do not need to solve a

three dimensional problem, instead the problem reduces to solving 3 one

dimensional problem.
In this case the part of the wave function that depends on the spatial coordinates

is,

  x, y, z    1  x   2  y   3  z 

The total energy,

E  E1  E2  E3