Quantum Physics, Lecture notes by Dr. S.

Karthikeyan

Unit 2: Quantum Physics

Dual nature of matter waves – De Broglie concept of matter wave-Group velocity and
phase velocity –Wave function-Continuity conditions-Schrodinger equation – time dependent
equation, time independent equation - Particle in a box.

Matter waves or de Broglie waves

In 1923, de Broglie proposed a new idea that matter must also show the wave-particle duality. The
wave associated with the matter is called as matter waves or de Broglie waves whose wavelength is
given by the following equation.

h h
l= =
p mv
P,m and v are the momentum, mass and the velocity of the particle. Since the wavelength is inversely
proportional to the mass of the particle, wave nature can be detected only for light particle such as
electron.de Broglie idea was confirmed by the Davisson and Germer experiment in 1927 and by G. P.
Thomson experiment.

Proof

From Einstein mass-energy relation,

E = mc 2
From Planck hypothesis,

We know that

E = hu
Comparing both equations, we have

hu = mc 2
c hc h h
h = mc 2 � l= = =
l mc 2
mc p
So the wavelength associated with the particle with a velocity, v is

h h
l= =
mv p

de Broglie relation for a non-relativistic particle

If the velocity of the particle is much smaller than the velocity of light, we can write

Page 1
 Quantum Physics, Lecture notes by Dr. S. Karthikeyan

1 2 m2v 2 p 2
E = mv = =
2 2m 2m

p = 2mE
Now the de Broglie relation becomes

h
l=
2mE
For a charged particle accelerated with a voltage (V), E = eV

h
l=
2meV
Phase velocity

It is defined as the rate at which the phase of the wave propagates in space. In terms of
frequency, the phase velocity is written as

V phase = nl

In terms of angular frequency w

V phase = w
k

k = 2p
l is known as wave vector.
For de Broglie (matter) waves, we can write

w h hu mc 2 c 2
V phase = = ul = u = = =
k mv mv mv v

c2
V phase =
v
Since the particle velocity is always less than the velocity of light, phase velocity of the
matter wave is greater than the velocity of light.

Group velocity

An ordinary plane wave with a definite wavelength cannot be used to describe a particle
which is localized within a narrow region. A large number of waves with slightly different
wavelengths combines and form a wave pocket which travels with a different velocity than

Page 2
 Quantum Physics, Lecture notes by Dr. S. Karthikeyan

the phase velocity of the individual wave. The velocity of the wave packet is the group
velocity. Wave pocket can represent a material localized at a given point. It can be proved that
the velocity of the particle is equal to the group velocity of the wave pocket associated with
the particle.

Group velocity is expressed as

dw
Vg =
dk
2
p2 h k2 h h 2p h h 2p
E = hu = h w = = Q E = hu = =
T 2p T
= h w and p = =
l 2p l
= hk
2m 2m

hk2
w=
2m
h 2kdk
Now dw =
2m

dw h 2 k h k p
= = = =v
dk 2m m m

dw
So we have proved that Vg = = v = velocity of the particle.
dk
Hence a particle can be represented as wave packet which is the superposition of a number of
wave trains and the group velocity is identical with the particle velocity.

Wave function

Wave function,y ( x, y, z , t ) is a complex function which gives the complete description of the
state of a particle quantum-mechanically.y ( x, y, z, t ) itself has no physical significance. But
the square of the wave function denotes the probability of finding a particle at a certain point
in space. This interpretation of y 2 was first given by Max Born in 1926. y ( x, y, z, t ) dV
2

represents the probability of finding a particle in a volume dV around the point ( x, y, z ) at

time t .

Since the particle has to be found somewhere, the sum of all the probabilities along the x-axis
(one dimensional case) has to be one.

Page 3
 Quantum Physics, Lecture notes by Dr. S. Karthikeyan

That is y ( x ) dx = 1 where y
�
2 2
= y *y
-�

In 3-dimensional case , we can write

�
y ( x, y, z ) dV = 1 where dV = dxdydz
�
2

-�

A wave function which satisfies this condition is said to be normalized.

An acceptable wave function should have the following properties.

1. Wave function gives all information about the state of a system

Continuity conditions:

2. Wave function must be a single valued function (one value at a point), finite and
continuous in all spaces.
3. The first derivative of the wave function must be continuous

Schrodinger wave equation

Schrodinger wave equations play an important role in Quantum Physics as do Newton’s law
of motion in classical mechanics.

Schrodinger time dependent wave equation

A plane wave is described by the wave function y ( x, t ) = Aei( kx -wt )

Replace k and ω by using the following relations

E = h w and p = hk and we have the wave function associated with a particle is

i
( px - Et )
y ( x, t ) = Ae h ---------- (1)

Differentiate equation (1) with respect to x

y ( x, t )
� i
�i � h ( px - Et )
= � p �Ae ---------- (2)
�
x �h �
Differentiate equation (2) with respect to x

�2y ( x, t ) �i � i
�i � h ( px - Et )
= � p�
� p �Ae
�x2 �h �
�h �

Page 4
 Quantum Physics, Lecture notes by Dr. S. Karthikeyan

�2y ( x, t ) �i 2 2 � hi ( px - Et )
= � 2 p �Ae
�x2 �h �

�2y ( x, t ) � p 2 � hi ( px - Et )
= �- 2 �Ae
�x2 �h �

�2y ( x, t )
-h 2
2
= p 2y ( x, t ) ---------- (3)
�x
Differentiate equation (1) with respect to t

y ( x, t )
� i
� i � h ( px - Et )
= �- E �Ae
�
t �h �

y ( x, t ) �1 � hi ( px - Et )
�
= � E �Ae (multiplying the R.H.S by (i/i))
� t �ih �

y ( x, t )
�
ih = Ey ( x, t ) ---------- (4)
� t

p2
The total energy E is written as E = +V ---------- (5)
2m

Substitute equation (5) in (4),

y ( x, t ) �p 2
� �
ih y ( x, t )
= � +V �
� t �2 m �

y ( x, t ) p 2y ( x, t )
�
ih = + Vy ( x, t ) ---------- (6)
� t 2m
Using equation (3) in (6)

y ( x, t )
� h 2 �y ( x, t )
2

ih =- + Vy ( x, t )
� t 2m � x2
It is the one dimensional, time dependent Schrodinger wave equation.

In 3-dimensions, it is given as

y ( x, y , z , t )
� h2 2
ih =- �y ( x, y, z , t ) + Vy ( x, y , z , t )
�t 2m

Page 5
 Quantum Physics, Lecture notes by Dr. S. Karthikeyan

�2 �2 �2
Where � = 2 + 2 + 2 is known as Laplace operator.
2

�x � y � z

Schrodinger time independent wave equation

Schrodinger time dependent equation is written as

y ( x, t )
� h 2 �y ( x, t )
2

ih =- + Vy ( x, t ) ---------- (1)
� t 2m � x2
The wave function associated with a particle is

i
( px - Et )
y ( x, t ) = Ae h

ipx iEt
-
y ( x, t ) = Ae e h h

ipx
Let us define y ( x) = e h
which is the function of x only

iEt
-
Now y ( x, t ) = Ay ( x ) e h ---------- (2)

Differentiate equation (2) with respect to x

y ( x, t )
� y ( x ) - iEth
�
=A e ---------- (3)
�x �x
Differentiate equation (3) with respect to x

�2y ( x, t ) �2y ( x ) - iEth

=A e ---------- (4)
�x2 �x2
Differentiate equation (2) with respect to t

y ( x, t )
� iE -
iEt
= - Ay ( x ) e h ---------- (5)
� t h
�2y ( x, t ) y ( x, t )
�
Substitute the value ofy ( x, t ) , 2
and in equation (1).
�
x �
t

� iE -
iEt
� h 2 � �2y ( x ) - iEth � -
iEt
ih �- Ay ( x ) e �= -
h
�A 2
e �+ VAy ( x ) e h
� h � 2 m � �x �

Page 6
 Quantum Physics, Lecture notes by Dr. S. Karthikeyan

� iE -
iEt � h 2 � �2y ( x ) - iEt � -
iEt
ih �- Ay ( x ) e h �= - �A e h �+ V Ay ( x ) e h
� h � 2m � �x 2 �
� � � �

� h ��y ( x ) �
2 2
� iE
ih �- y ( x ) �= - � 2 �+ Vy ( x )
� h � 2m � � x �

h 2 ��y ( x ) �
2
Ey ( x ) = - � 2 �+ Vy ( x )
2m � � x �

h 2 ��y ( x ) �
2

� 2 �+ ( E - V ) y ( x ) = 0
2m � � x �

��2y ( x ) � 2m
� 2 �+ 2 ( E - V ) y ( x ) = 0 ---------- (6)
�� x � h

Here ψ is the function of x only. The equation (6) is known as Schrodinger time independent wave
equation. In 3-dimensions,

2m
�2y ( x, y, z ) + ( E - V ) y ( x, y, z ) = 0 ---------- (7)
h2

Application of Schrodinger wave equation

Particle in a box
Let us consider a particle of mass m kept inside a box of infinite height with width L. The
particle is moving freely between the walls of the box and its potential is assumed to be zero
inside the box. Since the potential outside the box is infinite, the particle cannot escape from
the box.

Page 7
 Quantum Physics, Lecture notes by Dr. S. Karthikeyan

We can write

V =0 for 0 < x < L

V = � for 0 �x �L

Since the presence of particle outside the box is zero, we can write

At x = 0, y ( x ) = 0 ---------- (1a)

At x = L, y ( x ) = 0 ---------- (1b)

Equation (1a) and (1b) are known as boundary conditions.

Applying Schrodinger equation to this particle, we have

��2y ( x ) � 2m
� 2 �+ 2 ( E - 0 ) y ( x ) = 0 (V=0 inside the box)
�� x � h

��2y ( x ) � 2m
� 2 �+ 2 Ey ( x ) = 0
�� x � h
��2y ( x ) � 2
� 2 �+ k y ( x ) = 0 ---------- (2)
�� x �

2mE
Where k2 = ---------- (3)
h2
The solution of the equation (2) is given as

y ( x ) = A sin kx + B cos kx ---------- (4)

Applying boundary condition (1a) in (4), we get

0 = A sin ( 0 ) + B cos ( 0 )

B=0
Applying boundary condition (1b) in (4), we get

0 = sin kL
sin kL = 0
kL = np
np ---------- (5)
k=
L

Page 8
 Quantum Physics, Lecture notes by Dr. S. Karthikeyan

Where n=0,1,2,3,…..

Now the wave function becomes

np x �
�
y ( x ) = A sin kx = A sin � � ---------- (6)
�L �
To find the constant A

Since the total probability of finding the particle inside the box is one, we can write

L 2

y dx = 1
�
0

�np x �
L

� dx = 1
2 2
A sin � �
0 �L �

� �2np x �
�
1 - cos �
�
L �
�
A2 �� �L � �dx = 1
0�
2 �
�
� �
�

�2np x �
L
A2 � �
�1 - cos �
�
2 0� �L �
�dx = 1
�
�
L
� �2np x ��
2 � sin � ��
A �L �
x-
� �=1
2 � �2np � �
� � ��
� �L � � 0

A2
[ L - 0 - 0 + 0] = 1
2

A2 L
=1
2

2
A=
L
Now the equation (5) becomes

2 �np x �
y ( x) = sin � � ---------- (7)
L �L �
Substitute the value of k from equation (5) in (3)

Page 9
 Quantum Physics, Lecture notes by Dr. S. Karthikeyan

n 2p 2 2mE
k = 2 = 2
2

L h

n2 h2
En = ---------- (8)
8mL2

The energy value depends on some constants and n. n takes only positive integers. So the energy of
the particle in a box cannot take continuous value and is quantized. The integer, n is known as
quantum number. The value of energy corresponding to n=1, is the ground state or the lowest energy
of the particle in a box. According to quantum mechanics, the particle has a finite energy value even
at absolute zero.

Page 10