Unit.

3 Elementary Quantum Mechanics 9 hours

 

Wave –particle duality, de-Broglie hypothesis. Matter waves: properties of

matter waves, wave packet, group velocity, phase velocity and their relations.
Application of matter waves: SEM and TEM.
Uncertainty principle: Illustrations-Non-confinement of electron inside the
nucleus and broadening of spectral lines. Wave function, physical
significance of wave function, Eigen function, Eigen values; Application:
Quantum Computer (Classical BITS vs QBITS). One dimensional time
independent Schrodinger’s wave equation - particle in a box. Application of
Schrodinger’s wave equation: STM, Tunnel diode.
 Wave Function

• An equation that relates classical particle with its wave counterpart.

• The beauty of this equation lies in its simplicity!

• A few comments from noted physicists of that era:

“The most remarkable of all discoveries in 20th century”- Arnold Sommerfeld

“I am reading your communication in a way like a child eagerly listens to the

solution of a riddle with which he struggled for a long time, and I rejoice in the
beauty of what my eyes discover……!” – Max Planck.

“ Where did we get that equation from? Nowhere. It is not possible to derive from
anything you know. It came out of mind of Schrodinger, invented in his struggle
to find an understanding of the experimental observation of the real world”-
Richard Feynmann
 Wave Function

The varying quantity characterising the matter field or matter

waves is denoted by ψ(x) at a point x–direction. It is know as
wave function or wave amplitude.
 Physical significance of the wave function
The wave function ψ(x, t) is the solution of Schrö dinger wave equation
and quantum-mechanically describes the behavior of a moving particle.

The wave function ψ cannot be measured directly by any physical

experiment.

ψ gives a measure of the probability of finding a particle at a

particular position. ψ is also called the probability amplitude.

Itself has no physical meaning as it is complex and non observable

The probability density P (x,t) , product of the wave function ψ and

its
complex conjugate ψ*, is a measure of probability density i.e., probability
per unit volume of the particle being at a point.
2 2
P( x, t )    ( x , t )  
 Normalization of wave function
Consider a particle, represented by the wave function ψ, to be present in in a volume τ
If |ψ|2 d is the probability of finding the particle in a small volume dτ then
total probability of finding a particle anywhere inside volume τ must be 1 i.e.,

 d  1
2



This requirement is known as the Normalisation condition.

In one dimension the normalization condition is

 x
 2 dx  1

Note: When the particle is bound to a limited region the probability of finding the particle at infinity is zero i.e.,

 *  0 at x  
Properties of wave function

The wave function ψ should satisfy the following properties to describe the
characteristics of matter waves.
1. ψ must be a solution of Schrö dinger wave equation.
a
2. The wave function ψ should be continuous b
and single valued everywhere (x) (x)
3. Ψ is finite everywhere

4 The first derivative of ψ with respect to x P x P x

should be continuous and single valued
everywhere, since it is related to the
momentum of the particle which should be c
finite.
(x) d
(x)
5. Ψ must be normalized so that ψ must go
to 0 as x → ±  , so that ∫2 d over all the
space be a finite constant. R x Q x
Figure b, c, and d do not represent wave functions
Eigen functions and Eigen values
The physically acceptable solutions of SWE are called Eigen functions (ψ).

The physically acceptable wave functions ψ has to satisfy the following conditions:
1. ψ is single valued.
2. ψ and its first derivative with respect to its variable are continuous everywhere.
3. ψ is finite everywhere

Eigen values: The eigen functions are used in Schrö dinger wave equation to evaluate
the physically measurable quantities like energy, momentum, etc., these values are
called Eigen values. ^ ^
In an operator equation O    where O is an operator for the physical quantity and
ψ is an Eigen function and λ is the Eigen value.
For example : 
H   E
H → total energy (Hamiltonian) operator, ψ → Eigen function and E → total energy in the
system.
for the momentum

P   p
P → momentum operator and p → momentum eigen values.
 Schrödinger’s Wave Equation
• A consequence of wave particle duality
• The Schrödinger wave equation, a partial
differential equation,  is the fundamental equation of physics
for describing quantum mechanical behavior.
•It describes the time-evolution of wave function for a given
physical system
• SWE is the quantum mechanics analogue to the Newton's laws
Erwin Schrödinger of motion
Nobel Prize 1933
SWE cannot be derived from any basic principles, but can be arrived at, by using the
de-Broglie hypothesis in conjunction with the classical wave equation

A wave function in quantum physics is a mathematical description of the quantum state of a

system, whose variation gives matter waves
Time Independent one dimensional Schrödinger wave equation
Let ψ(x,t) be the wave function of the matter wave associate with a particle of
mass ‘m’ moving with a velocity ‘v’. The differential equation of the wave motion is
as follows.
 2 1  2
 .....(1)
x 2 v 2 t 2
The solution of the Eq.(1) as a periodic displacement of time ‘t’ is

ψ(x,t) =ψ0(x) e-iωt …..(2)

ψ0(x) → amplitude of the matter wave

Differentiating Eq.(2) partially twice w.r.t. ‘t’, we get


 i 0 ( x ) e it
t
 2 2 2  i t 2 it 2
 i   0 ( x ) e     0 ( x ) e   ( x )
t 2
 2 2
2
  .....(3)
t
Let us substitute Eq.(3) in Eq.(1)
  2 2
 2  ....(4)
x 2 v
2
 2
 2  4 2
We know that 2
 k  
2
  2

v    
 2 4 2
Substituting this in Eq4, we get 2
 2  ....(5)
x 
 2  4 2
2
 2 0 ....(6)
x 

From de-Broglie wavelength we have h


mv
 2 2 2
2 m v
2
 4 2
0 .....(7)
x h
The kinetic energy of the particle with total energy E and potential energy V is
1
Ek  mv 2  E  V
2
Substituting this in Eq.7,
2 2
 m v  2m ( E  V ) we get the
Schrödinger time- independent one dimensional wave equation

 2  8 2 m
2
 2 ( E  V )  0
x h

Here ψ is a function of x alone and is independent of time

  
Schrodinger's time dependent wave equation

The solution of the classical differential eqn. of wave system is,   e 0

 it

Differentiating the above equation with respect to time ‘t’ ,


 i 0 e  it  i
t

Substituting E = h   2
  E 
 i 2 v  i 2  
t  h 

 E E h
 i 2v  i   i 2
  since  
2
t   i 

E  i 
t

2m
 2  ( E  V )  0
2
2m 2m
 2  2
E  V  0
 2
12
 2m  2m
 2  2
i   2
V  0
 t 

2
Multiply
2m

2 2
   E  V  0
2m
2 2
    V  E (Time dependent Schroedinger wave eqn)
2m
The Hamiltonian operator
2 2
H   V
2m

H  E
E  energy operator
H  Hamiltonian
13
 Applications of Schrodinger’s wave equation
1. Particle in an one-dimensional potential well of infinite depth (Particle in a box)
Let us start with a particle of mass ‘m’ moving freely in x- direction in the region from x=0 to x=a.
The potential energy V(x) =  for x<0 and x>a
V(x) = 0 for 0 ≤ x ≤ a

2 2
  8 m
Outside the box Schrodinger’s wave equation is
2
 2  E      0............(1)
x h
2
Where  =0 for all points outside the box i.e.,   0  particle cannot be found at all outside the box

Inside the box V = 0, the Schrodinger’s equation is given by,  

 2  8 2 m
 2 E  0 Region I Region II Region III
x 2 h

 2
2
 k 2   0..............( 2)
x
V= V=0 V=

8m 2 E
where k2  ............(3)
h2

The solution of equation (2) is   A cos kx  B sin kx..........(4) x=0 x x=a

where A & B are constants which depends on the boundary conditions of the well.
 applying boundary conditions

Condition: I at x =0,  = 0.
Substituting the condition I in SWE solution, we get A =0 and B0
(If both A and B = zero for all values of x, then ψ is zero. Which means the particle is not present in the well)

equation (3) can be written as   B sin kx..........(5)

Condition: II at x =a,  = 0
Substituting the condition II in Eq (5) we get
0= B sin(ka)
since B  0
sin ka  0
 ka  n where, n = 1,2,3…………….
n
k
a
n 22
2
k  2
a
 2 8m 2 E
Now we have k 
h2
2 n 2 2
k  2
a

On equating and n2 h2
simplifying we get
E
8ma 2

The above equation gives the energy values or Eigen values of the particle in the well.

When n=0, n = 0. This means to say that the particle is not present inside the box,
which violates our initial assumption. Hence n0 and the lowest value of ‘n’ is 1.
 The lowest energy corresponds to ‘n’=1 is called the zero-point energy or Ground
state energy. 2
h
E zero  po int 
8ma 2
All the states of n  1 are called excited states.
Now its time to evaluate B by normalization of wave function.
Normalization of wave function :
n
  B sin kx  Bsin x
a
As there is only one particle within the box, the probability of finding the particle is 1.
a a
2 n
  dx  1
0
B 2

0
sin 2

a
xdx  1

1
w.k.t sin 2   1  cos 2
2
a a
B2  2nx  B2 
a a
2nx  B2  a  2nx 
2 0  2  0 0
 1  cos dx  1  dx  cos dx   1  x  sin    1
a  a  2  2n  a  0

B2  a
   B2a 2
a 
 2n sin 2 n  0   1 1 B
2 2
a
Thus the normalized wave function of a particle in a one-dimensional box is given by,

2  n  where, n=1,2,3……………
n  sin  x
a  a 

This equation gives the Eigen functions of the particle in the box. The Eigen functions for
n=1,2,3.. are as follows.

2 
1  sin   x
a a

2  2 
2  sin   x
a  a 

2  3 
3  sin   x
a  a 
Eigen functions and Eigen values
Case (1): n=1.
Ground state and the particle is normally found in this state.
For n=1, the Eigen function is 1
2

2 
1  sin   x
a a x=0 x=a/2 x=a
1 =0 at x=0 & x=a
1 has a maximum value for x=a/2.
2 a 2
1  sin   
a a2 a 1

|1|2 → the probability density 2 x=0 x=a/2 x=a

2
|1|2 =0 at x = 0 and x = a,  
1
a
|1|2 is maximum at x = (a/2)

At ground state the particle cannot be found at the walls of the box and the probability of
finding the particle is maximum at the central region.

h2
The Energy in the ground state is given by E1 
8ma 2
 Case 2: n =2 → the first excited state.

The Eigen function for this state is given by

2  2 
2  sin   x
a  a 

In the first excited state the particle cannot be observed either at the walls or at the
center
The energy is E2=4E1
Case 3: n =3 the second excited state
The eigen function for this state is given by

2  3 
3  sin   x
a  a 

|3|2=0 for the values x=0, a/3, 2a/3, a and |3|2 reaches maximum 2/a at x=a/6, a/2,
5a/6 at which the particle is most likely to be found.

The energy corresponding to second excited state → E3=9E1

.
Applications of Schrodinger’s wave equation contd…

2. Free Particle:
A particle, which is not under the influence of any kind of field or force.
Thus, it has zero potential, i.e., V=0 over the entire space.

Hence Schrodinger’s equation becomes,

 2  8 2 m
2
 2 E  0
x h
h   2 
 2  2   E
8 m  x 

The above equation holds good for a particle for which the potential V=0 over the entire space

Let us extend the case of particle in an infinite potential well to the free particle case, by
treating the width of the well to be infinity, i.e., by allowing a =

n 2h 2
E where n = 1, 2, 3…
8ma 2
 Practice Problems

1. An electron has a speed 400 m/sec. with uncertainty of

0.01%. Find accuracy in its position.

Sol: velocity v = 400 m/sec

 Δv = 400 x 0.01% = 0.04

Δx. Δv =

Ans: 0.0029 m
2. Find the eigen function and eigen values for wave
functions ψ(x) = e4x

Sol: 2
 
2
(e 4 x )  4 (e4 x)  16(e4 x)
x x

2
Here x 2 is the operator, e4x
3. An electron is bound in one-dimensional box of size 4 x 10 -10m.
What will be the minimum energy?

Sol: The quantized energy levels of a particle in one-

dimensional box of size ‘a’ is
Sol: The quantized energy levels of a particle
in one-dimensional box of size ‘a’ is
En =
Calculate the energy required for an electron to jump from ground
state to the second excited state in a potential well of width L

Sol: - =
A particle is moving in 1D potential box of width 50 Å. Calculate the
probability of finding the particle within an interval of 2.5 Å at the
centres of the box when it is in its state of least energy.

Sol: 2  n 
n  sin  x
a  a 

For least energy state n = 1, sin

At the center of the box x =

The probability of finding the particle in the interval at the center of the box is [ψ(x)]2 =
sin ] = 2/a

The probability P in the interval Δx is P = [ψ(x)]2 = Δx

Given: a = 50 Å. Δx = 5 Å