QM
QM
QM
Karthikeyan
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
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
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
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.
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
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
-�
-�
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
i
( px - Et )
y ( x, t ) = Ae h ---------- (1)
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
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
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)
y ( x, t )
� y ( x ) - iEth
�
=A e ---------- (3)
�x �x
Differentiate equation (3) with respect to x
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
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
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)
��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
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,…..
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