Introduction to Nanotechnology

Module: 1
Numerical on de Broglie’s hypothesis
 𝒉 𝒉 𝒉 𝒉
𝝀= = = =

√
𝒑 √ 𝟐 𝒎( 𝑲 . 𝑬 ) 𝟑 √ 𝟑 𝒎𝒌𝑻
𝟐𝒎 𝒌𝑻
𝟐
 WAVE FUNCTION
&
SCHRODINGER'S WAVE EQUATION
 WAVE FUNCTION
A variable quantity which characterizes de Broglie waves is known as wave function.
The wave function is represented by the symbol 

The value of the wave function associated with a moving particle at point (x, y, z) and time
‘t’ gives the probability of finding the particle at that time and at that point.
 WAVE FUNCTION
PHYSICAL SIGNIFICANCE OF WAVE FUNCTION
 The wave function has no physical meaning.

 It is a complex quantity representing the matter wave of a particle.

 ψ×ψ*= │ψ │2 is real and positive, amplitude may be positive or negative, but the intensity(square of
amplitude) is always real and positive.

 ψ×ψ*=│ ψ │2 represents the probability density or probability of finding the particle in the given
region.

 The probability P = ∫ ∫ ∫│ ψ │2 d where d =dx dy dz

 ∫ ∫ ∫│ ψ │2 d= 1, this wave function is called normalized wave function.

 ∫ ∫ ∫│ ψ │2 d= 0 , it is the orthogonalization condition

 The probability value lies between 0 and 1.

 Physical significance of the wave function
The wave function ψ(x, t) is the solution of Schrödinger 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 )  
 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 Schrödinger wave equation.
a b
2. The wave function ψ should be continuous and
single valued everywhere (x)
(x)

3. Ψ is finite everywhere
P x
4 The first derivative of ψ with respect to x should be P x
continuous and single valued everywhere, since it is
related to the momentum of the particle which should
be finite.
c
5. Ψ must be normalized so that ψ must go to 0 as x → d
(x) (x)
±  , so that ∫ d over all the space be a finite
2

constant.

R x Q x
Figure b, c, and d do not represent wave functions
 SCHRODINGER'S WAVE EQUATION

 Describes the wave nature of a particle , derived in mathematical form

 Two forms of Schrodinger's wave equation

Time Independent wave equation

Time dependent wave equation
 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
behaviour.
•It describes the time-evolution of wave function for a given physical system
Erwin Schrödinger
Nobel Prize 1933 • SWE is the quantum mechanics analogue to the Newton's laws of motion

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

state of a system, whose variation gives matter waves
 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  
*
Schrödinger time- independent one-dimensional wave equation

  8 m
2 2
 2 ( E  V )  0
x 2
h
Here ψ is a function of x alone and is independent of time

2 2
𝜕 𝜓 8𝜋 𝑚
2
+ 2
(𝐸 −𝑉 )𝜓=0
𝜕𝑦 h

2
2 8 𝜋 𝑚
𝛻 𝜓 ( 𝑟 ) + 2 (𝐸 − 𝑉 )𝜓(𝑟)=0
h
=+
 Eigen functions and Eigen values
The physically acceptable solutions of SWE are called Eigen functions (ψ).
The physically acceptable wave functions ψ must 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.
Example : In an operator equation
where is an operator for the physical quantity and is an Eigen function and λ is the Eigen value.

Example2: Energy 

Operator H   E
H → total energy (Hamiltonian) operator, ψ → Eigen function and E → total energy in the system.
Example3: 
Momentum P   p
Operator
P → momentum operator and p → momentum eigen values.
 Applications of Schrodinger’s wave equation(1-D box)  2  8 2 m
 2 ( E  V )  0
1. Particle in an one-dimensional potential well of infinite depth (Particle in a box) x 2
h
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
Region I Region II Region II
V(x) = 0 for 0 ≤ x ≤ a
Outside the box Schrodinger’s wave  2  8 2 m
equation is
 2 E     0............(1)
x 2
h
 particle cannot be found at all V= V=0 V=
Where  =0 for all points outside the box i.e.,  2  0
outside the box

Inside the box V = 0, the  2  8 2 m x=0 x x=a

Schrodinger’s equation is given by,  2 E  0
x 2
h

 2
 k 2
  0..............( 2)
x 2

8m 2 E
where k 
2
............(3)
h2
The solution of equation (2) is   A cos kx  B sin kx..........(4)
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
k  2
2

a
 8m 2 E
Now we have k 
2

h2
n 22
k  2
2

On equating and n 2h 2
simplifying we get E 2
................(6)
8ma
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.

h2
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
n
p    dx  1
2
B  sin
2 2
xdx  1
0
a
0
1
w.k.t sin 2   1  cos 2
2
2 a
B  2nx  B2 
a a
2nx  2
B  a
a
 2nx 
2 0 1  cos a dx  1   dx   cos
2 0 0
a
dx   1
 2  2n  a   1

x  sin
  0

B2  a  B2a 2
a 
 2 n 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 
n  sin  x where, n=1,2,3……………
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.
2
For n=1, the Eigen function is 1

2 
1  sin   x x=0 x=a/2 x=a
1 =0 at x=0 & x=a a 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

|1|2 =0 at x = 0 and x = a,  
2
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.

The Energy in the ground state is given by h2

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 E  0
x 2
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
 Particle in a 3-D box :
2 2 2
(𝑛¿ ¿ 1 + 𝑛 +𝑛 )h 2
2 3
𝐸𝑛 𝑛 𝑛 = ¿
1 2 3
8 𝑚𝑎2
E0
Where n1 = 1, 2, 3, ………..
n2 = 1, 2, 3, ………..
n3 = 1, 2, 3, ………..
(12+12+12)E0 = 3E0
3

= (12+22+12)E0 = 6E0
= (22+12+22)E0 = 9E0