QUANTUM

MECHANICS
Erwin Rudolf Josef Alexander Schrödinger
(1887 –1961)

one of the fathers of quantum mechanics,

the Schrödinger equation,

- he received the Nobel Prize in Physics in 1933.
In 1935,
after extensive correspondence with personal friend
Albert Einstein,
he proposed the Schrödinger's cat thought experiment.
The wave Equation ( Schrodinger’s equation)- time dependent
Fundamental equation of Quantum Mechanics
(like second law motion of Newtonian mechanics F=ma)
Is a wave equation in the variable 

For standing wave equation in classical

y = A cos ( t  kx ) 1

Let us consider the wave equivalent of a Free Particle in a straight path at

constant speed

This wave is described by general solution

y = A cos ( t  kx )  i A sin ( t  kx ) 2

(If undamped, monochromatic harmonic wave in + x direction)

2 can be written in the for

y  Ae  i (t - kx )
Only real part of (2) has significance in the case of waves in a stretched string.
‘y’ means displacement , imaginary is discarded as irrelevant.

In quantum mechanics the wave function ‘’ corresponds to the wave

variable ‘y’ of wave motion in general.

However,  - is not measureable quantity and may therefore be complex

  Ae i (t - kx )
It convenient to change  and k in terms of total energy ‘E’ and momentum
‘p’ of the particle being described by ‘’
i
  Et  px 
  Ae 
-3
Since
E= h = 2 * h/ 2 = ħ 
E= ħ  =E/ ħ
 =h/p p =h/  = = (h/ 2)* (2 / )
 P= ħk k = P/ ħ
(3) describes the wave equivalent of an unrestricted particles
of total energy ‘E’ and momentum ‘p’ moving in + x direction
Wave function ‘’ given by (3) is correct only for free moving
particle
However motion of particle with various restriction are
interested
 e.g. Electron bound to an atom by electric filed of nucleus
A particle can have as a wave only under motion,

So the total energy E of the particle is sum of K.E and its potential energy U,
Where U is in a function of position ‘x’ and time ‘t’

1 2
E  mv  U ( x, t )
2
2 2
1mv
E U
2 m
p2
E U -(4)
2m
multiplying both side of eq. 4 with wave function 
p2
E    U -(5)
2m
Aim to obtain the fundamental differential equation for ‘’

- solve for ‘’ in a specific situation

Differentiating eq. 3 for ‘’ twice w.r.t ‘x’

 ip  i  Et  px  ip
 Ae  
x  
 i p
2 2 2

i
 Et  px  p 2
 Ae 
 2
x 2
 2

 2

p   
2 2

x 2 ------- 6

differenti ating eq.3 once w.r.t. ' t'

 iE  i  Et  px  iE
  Ae  
t  
  
E    E  i
i t t ------7
Substitute ‘E’ and p2 

  2  2 -(8)
i   U
t 2m x 2
in three dimensions the time - dependent form of schrodinger eq.
  2   2  2  2 
i   2  2  2   U
t 2m  x y z 
   2 2 
i      U 
t  2m  -(9)
E  H

E  i  energy operator
t
 2 2 
H      U   Hamiltonian operator
 2m 
Schrodinger’s time independent equation
Let us consider a system of stationary wave associated a moving particle.
Let  be the wave function of particle along x.

For simplicity we take 1 dimension Cartesian coordinate

i
  Et  px 
then
  Ae
x ,t
 ----- 3
ip
x
Removing time component
  Ae x
 ----- 4

Differentiating eq. 4 w.r.t. x

 x ip i
px ip
 Ae   x
x  
 2 x i 2 p 2 i
px p 2
 Ae 
  2 x
x 2
 2

 2
x
p  x  
2 2
-(5)
x 2
 p2
E U
2m
multiplying both side of eq. 4 with wave function x
p2
E x   x  U x
2m
-(6)
1  2  2 x 
E x       U x
2 
2m  x 
  2  2 x
E x   U x
2m x 2

  2  2 x
 E  U  x 
2m x 2
2m  2 x
 E  U  x   2
 2
x
 2 x 2m
  2  E  U  x
x 2

if in 3 dimention
 2 r  2 r  2 r 2m
    2  E  U  r
x 2
y 2
z 2

2m
  r   2  E  U  r
2


  laplacian operator
therefore
2m
  r  2  E  U  r  0
2


Schrodinger equation obtained here is for wave function of
a freely moving particle

Then how far it applies to general case of particles subject

To arbitrary forces

Postulate Schrodinger eq. , solve it for a variety of physical

situation , compare the results of cal. And exp.

Both agree -> postulate is valid

Not agree-> postulate must be discarded and some other
approaches have to be explored

Schrodinger’s eq. cannot be derived from other basic principles

Of physics ; it is a basic principle in itself.

Remarkably accurate in predicting the results of exp.

Used only for non-relativistic problem
Elaborate formulation needed for relativistic

newton’s second law F=ma

Application of Schrodinger’s eq.
Particle in a Box or Infinite potential well
To solve Schrödinger eq. elaborate mathematics is needed

Simplest quantum mechanical problem

- particle trapped in a box with infinitely hard wall

Let us consider
- motion of a particle
along x – direction
within the region x= 0 and x= L
rigid walls of infinite height
- particle does not loss energy when it collides on walls

- potential energy is constant V(x) = 0 ; 0 < x < L

- potential energy is infinite V(x) =  at x=0 and x = L ( 0xL)

Particle cannot have infinite energy so, it can not exist outside the box.

- rectangular potential box or potential well

of infinite depth and width L
 Our task is to find what  is with in the box
Height - 

U(x)=  U(x) = 0 U(x) =

x=0 x=L
Time independent Schrodinger ‘s equation for free particle

 2 2m
 2  E  U   0
x 2

we have taken U(x)  0
 2 2m
 2 E  0
x 2

d 2
2
 k 2
 0 Total derivative is the same as partial
dx Derivative becs,  is the function only
Of x
2m
where k  2 E
2


 ( x)  A sin kx  B cos kx
A and B are constants to be determined from boundary conditions

At x = 0, =0

0 = A sin k 0.0 + B cos k 0.0

0 = B -> (x) = A sin kx

And At x = L then =0 => 0 = A sin kL

A = 0 is meaning less, ie it means that no wave

kL = n ; where n = 1,2,3…..
k = n / L

Ö(2mE/ ħ2 ) = n / L

Energy of particle can not be any arbitrary values,

It can have only certain discrete values

2m n 2 2
2
En  2
 L
n 2 2  2
En  2
where n  1,2,3.... ; are energy eigen valu es
2mL

N=0 is excluded since E0=0 then  become ‘Zero’ which not

permissible physically and quantum mechanically

It s energy is quantized.
 Wave function of particle in a box whose energy En with B=0

2mEn
 ( x)  A sin x

n
 ( x)  A sin x
L

For each n,  is a finite, single valued function of ‘x’

n and dn/dx are continuous

Integral of | n |2 for over all space is finite.

To normalize  we have to assign the value of A





 ( x) 2 dx  1
L


0
 ( x) 2 dx  1

 n 
L
A  sin 
2
x dx  1
2

0  L 
A   n  
2 L L

  dx   cos 2 x dx   1 ; from trignamet ry;

2 0 0  L  
2 L
A   L   2n  1
 x  sin  x   1 sin   (1 - cos2 )
2

2   2 n   L  0 2
2
A 2
 L  1  A 
2 L
 The normalized wave function of the particle

2 n
n  sin x n  1,2,3....
L L
0.4 0.4
0.2 0.2
0.0 4 |4|2 0.0
-0.2 -0.2
-0.4 -0.4
0.4 0.4
0.2 0.2
0.0
-0.2 3 |3|2 0.0
-0.2
-0.4 -0.4
0.4 0.4
0.2 0.2
0.0 0.0
-0.2 2 |2|2 -0.2
-0.4 -0.4
0.4 0.4
0.2 0.2
0.0 1 |1|2 0.0
-0.2 -0.2
-0.4 -0.4
0 2 4 6 8 10 0 2 4 6 8 10
A A
At particular place in the box the probability of the
particle Being present may
Vary for different quantum number

For instance |1|2 has its max. at L/2 (middle of box)

For instance |  2|2 has its 0 . at L/2 (middle of box)

Classical mechanic suggest the same probability for

the Particle being anywhere in the box

The wave function resemble the stretched string fixed

both ends

-same form of equation

 Find the probability that a particle trapped in the box L wide can be
Found between 0.45L and 0.55L for the ground and first exited states

x2
Px1, x 2  
x1
 ( x) 2 dx

2  n
x2
2 
  sin  x dx
L x1  L 
x2
 x  1   2 n  
    sin  x 
 L  2n   L  x1

n= 1 P x1,x2 =0.198 then 19.8 percent

n= 2 P x1,x2 =0.0065 then 0.65 percent
 A eikx + B e-ikx
 A coskx + iA sinkx +B coskx – iB sinkx

 (A+B) coskx + i(A-B)sinkx

 C1 coskx+C2 sinkx