UNIT I

QUANTUM MECHANICS

Wave particle dualism

It is bit difficult to conceive the idea of conception of dual nature of matter. i.e.,
matter behaves as both particle and wave nature.
The characteristics of a particle are: it has a mass, it occupies a definite point on a
space, it can move from one point to another point. So it has momentum. Thus the
particles can be specified by
a) mass b) velocity c) momentum d) energy and e) two particles cannot occupy a
single space simultaneously. A wave is specified by
a) wavelength b) frequency c) amplitude d) Intensity and e) phase
Thus the characteristics of particles are quite different from those of wave. But
from the experimental facts it has been established that the radiations such as light some
time behave as wave and some time as a particle.
To explain the phenomenon such as interference, diffraction, etc. a radiation
should behave as wave. To explain photoelectric effect, Compton Effect, etc. the radiation
should behave as particle (photon).
Thus radiation has dual nature. But it is to be noted that the radiation cannot
exhibit both the properties of particle and wave simultaneously.

De Broglie’s concept of matter wave

The origin of quantization of energy lies in the dual behavior observed in nature in
particle and wave aspects. Consider x – rays, Compton observed that the scattering of x –
rays by electron is the confirmation of law of conservation of energy and it is a case of
elastic collision of two particles. So from the physics point of view, x – rays assumes the
status of a particle. Also x – rays are diffracted by a crystal. Since diffraction is a wave
phenomenon, x – rays behaves as waves. Because of this dual nature of radiation, Louis
de Broglie in 1924, given an hypothesis which states that “since nature likes symmetry, if
the radiation behaves as particle under certain circumstances, and as waves under certain
other circumstances, then one can even expect that entities which ordinarily behave as
particles to exhibit properties attributable to only waves under appropriate circumstances
h
and he termed them as matter waves”. The de-Broglie wavelength λ =
p

1
De Broglie wavelength of an accelerated electron:
If the electron accelerated under the potential difference V, then its energy is eV. If
m is the mass of the electron and v is its velocity then for non relativistic case,

1 2 2eV
m v  eV => v 
2 m

Following the de Broglie hypothesis,

h h h
  
p mv 2eV
m
m
h
So, 
2meV

Which can be written as,

1  h 
  
V  2me 

Substituting all the values,

1  6.63x1034 
i.e.,   
  31 19 
V  2 x9.11x10 x1.6 x10 

1.226 x109 12.26

 m OR  Å
V V

Relation between kinetic energy and de Broglie wavelength

1
Since Kinetic energy of an electron is given by E  m v2
2
So E = eV

h h h
   
2meV 2mE OR 2mE

2
Phase velocity

X
M N
mass(m) x

Let us consider traveling waves, which are set up in a spring which is oscillating
along Y – direction and moving with a uniform velocity ‘v’ along X – direction.
The equation for displacement at ‘N’ is given by

Y = A Sin ω t

Where A – Amplitude, ω – Angular frequency, t – time of crossing

Now the equation for displacement at M is to time earlier
Y = A Sin [ω (t – to)]
If ‘x’ is the distance between M and N then
x x
v= or to 
to v
x 
 Y = A Sin [ω (t - ) ] = A sin [ω t – ( ) x ]
v v
or Y = A sin (ω t – kx )

where k = called propagation constant or wave number
v

and v = is the velocity with which the wave disturbance is carried and is referred to as
k
phase velocity. Hence phase velocity is written as

vphase =
k

3
Definition: If a point is imagined to be marked on a traveling wave, then it becomes a
representative point for a particular phase of the wave, and the velocity with which it is
transported owing to the motion of the wave, is called phase velocity.

Group velocity:
Group velocity is the velocity with which the envelop enclosing a wave group
called wave packet formed due to superimposition of two or more traveling waves of
slightly different wavelengths is transported or it is the velocity with which the energy
transmission occurs in a wave packet.

a) Individual Waves b) Amplitude variation after

Superposition

Let us consider two traveling waves of same amplitude but of slightly different in
wavelengths and frequencies. The displacement along y – direction is given by
Y1 = A sin (ω t – kx ) -------------------------------(1)
Y2 = A sin [(ω +Δ ω )t – (k + Δ k)x] --------------(2)
Where A – common amplitude
 and (   ) are the angular velocities
k and (k + k ) are the wave numbers
x is common displacement, at the instant ‘ t’,
 and k are increments in angular velocity and wave numbers and are assumed to be
small.
The resultant displacement Y due to the superposition of two waves is given by

Y = Y1 + Y2

∴ Y  A sin(  t  kx)  A Sin [(   )t  (k  k ) x]

4
  A  B  A  B
using sin A + sin B = 2 cos   sin  
 2   2 

    k    2     2k  k  
Y = 2A cos  t    x  sin  t   x
2  
we get
 2   2    2  
since Δω and Δk are small

i.e 2ω + Δω ≈ 2ω and 2k + Δk ≈ 2k

    k  
Y = 2A cos  t    x  sin (ωt – k x) ----------------(3)
 2   2  

Comparing equation (1) and (3), the amplitude of the wave packet is

    k  
2A cos  t    x  ----------------(4)
 2   2  

Which is not a constant, but varies with wave. The velocity with which the
variation in amplitude is transmitted in the resultant wave is called group velocity and is
given by


vgroup = 2 = -----------------------------------(5)
k k
2

    d 
In limits  →  
 k   dk 

d
vgroup = ---------------------------------(6)
dk

This is the equation for group velocity

5
Relation between vgroup and vphase
We have the equations for group velocity and phase velocity as
d
vgroup = --------------------- (1)
dk

vphase = -------------------- (2)
k
Where ω – angular frequency, K – wave vector,

From (2), ω = k . vphase

d d (k .v phase )
vgroup= =
dk dk

dv phase
vgroup= vphase +k..
dk
Above equation can be written as

 dv phase  d 
vgroup = vphase + k    ------------------------ (3)
 dk 
 d  

2  2f 2
We know that, k = , k   
 v f 
Differentiate w.r.t. λ, we get
dk 2 d 2
∴  2 or 
d  dk 2

 d   2    
2
∴ k    .    -------------------------- (4)
 dk      2 
Use equation (4) in above equation
 dv phase 
vgroup = vphase -   

 d  
This is the relation between group velocity and phase velocity.

6
Relation between vgroup and vparticle

d
We know that, vgroup = --------------------- (1)
dk

E
But ω= 2πγ = 2π --------------------- (2) (since E = hγ)
h
2
∴ dω = dE -------------------- (3)
h

2 P h
Also, we have k =  2 (since λ = )
 h P
 2 
∴ dk =  dP ------------------ (4)
 h 

Equation (3) divided by equation (4)

d dE
 ----------------- (5)
dk dP

P2
We know that E=
2m
where P → momentum of a particle

2 P dP P dE P
∴ dE =  .dp or 
2m m dp m

but P = m v particle
dE mv particle
∴   v particle -------------------- (6)
dp m

From equations (1), (5) and (6) we have

vgroup = vparticle

∴ The de Broglie wave group associated with a particle travels with a velocity equal to the

velocity of the particle itself.

7
Relation between velocity of light, vgroup and vphase

We know, vphase =
k

E 2 P
Substitute ω = 2πγ = 2π and k =  2
h  h

2 E 2
∴ vphase = h  E  mc ∵ vgroup = vparticle
2 P P m v particle
h

c2
vphase =
v group

∴ vphase. v group = c2

Particle velocity is always less than ‘c’,  the phase velocity is always greater than ‘c’

Derivation of De-Broglie wavelength using vgroup

According to de Broglie, a wave packet has both group velocity and phase velocity.
d
We know that vgroup = ----------------------(1)
dk

2
But   2πγ and k =


1
 dω = 2πdγ and dk = 2πd( )


Equation (1) becomes

d
vgroup =
1
d( )


8
 1 d
or d( ) = ------------------ (2)
 v

If the particle has both kinetic energy and potential energy then total energy is given by
1 2
E mv  V ----------------- (3)
2
where ‘m’ is mass of the particle, ‘v’ is the velocity, and ‘V’ is potential energy.
Also E = h γ -------------------(4)
Where γ → frequency associated with particle.

∴ from equation (3) and (4)

1 2
hγ = mv  V --------------(5)
2

Let the particle is moving in a field of constant potential, ‘V’ is constant, and then
differentiate equation (5)
h.dγ = mv dv
m
or dγ = ( )v.dv -----------(6)
h
Substitute equation (6) in equation (2), we get
1 m
d ( )  ( ).dv
 h
After integrating we get
1 m
 ( )v  cons tan t
 h

Let ‘P’ be the momentum of the particle, i.e., P = mv, and let constant of integration be
zero.
1 p

 h
Then
h
or 
p

This is the de Broglie equation.

Characteristics of matter waves

9
The characteristics of matter waves are

i) Matter waves are the waves that are associated with a moving particle. The
wavelength and frequency of the waves are
h E
 and  where ‘h’ is planck’s constant.
p h

ii) The amplitude of the matter waves at a particular region and time depends on
the probability of finding the particle at the same region and time.

iii) The wave velocity or the phase velocity of the matter wave are given by
c2
v phase 
v group
where, vgroup is the particle velocity which is always less than ‘c’. Thus the
velocity of the matter waves is always greater than ‘c’, i.e., they are not physical
waves.

iv) Unlike any electromagnetic waves, which always travel with a constant
velocity c, the wave velocity of different matter waves may differ depending on
the mass and velocity of the particle.

Heisenberg’s Uncertainty Principle

10
 According to de Broglie, a particle can be considered as a group or packet of
waves. As this wave packet is spread in space, we cannot accurately find the position of a
particle. It can only said that, the particle is somewhere within the region over which the
wave packet is spread.
Let the motion of the particle be along x – axis. Let Δx is the distance at which the
amplitude is zero and corresponding points are called nodes. There will be a minimum
error ‘Δx’ in the measurement of the position of the particle. This is inevitable due to the
wave nature of matter.
  k 
The amplitude of the wave packet is given by 2 A cos( )t  ( ) x
 2 2 
At nodes, the amplitude is zero.
  k 
i.e., 2 A cos( ) t  ( ) x = 0
 2 2 

  k 
since 2A ≠0,  cos( )t  ( ) x  0
 2 2 
 k  3 
or ( ) t  ( ) x  , , ..............(2n  1) x
2 2 2 2 2
If x1 and x2 are the positions at which the nodes are formed, then for the first node.
 k 
( ) t  ( ) x1  (2n  1) ------------------------- (1)
2 2 2
Since, there is a change of phase π, between the successive nodes, the eaquation for the
second node is,
 k 
( ) t  ( ) x2  (2n  1)   --------------------- (2)
2 2 2
Subtracting equation (1) from equation (2), we get
k
( x1  x2 )   sin ce x1  x 2  x
2
k 2
(x)   or x  ----------------------- (3)
2 k
2 2Px 2 (Px )
we know that, k=  or k  ----------------- (4)
 h h
where ΔPx represents the fundamental error in the measurement of momentum of the
particle.
Substitute equation (4) in equation (3), we get

11
 h
x 
Px
This is the case of superposition of two waves. In general if there are more than two
waves.
1
x  2 ---------------- (5)
k
Substitute equation (4) in equation (5)
h
x 
4 (Px )
h
or x . Px  ----------------(6)
4
The fundamental error in ‘x’ and ‘Px’ could be equal to, or greater them Δx and ΔPx
respectively, then equation (6) can be written as
h
x . Px  ----------------(7)
4
Statement
“In any simultaneous determination of the position and momentum of the particle,
the product of the corresponding uncertainties inherently present in the measurement is
h
equal to, or greater than ( ) ” OR
4
“It is impossible to measure both the position and momentum of a particle
simultaneously”

Physical significance of Heisenberg Uncertainty principle

By knowing the particle position and momentum at any given instant of time, it is
possible to evaluate it position and momentum at any later point of time, and the trajectory
of the particle could be continuously traced. But in wave mechanics it is impossible to
determine simultaneously both the position and momentum of a particle accurately.
Suppose if we made the measurement of position of the particle such as electron very
accurately, then there is a large uncertainty in the measurement of momentum, and vice
versa. So one should not think the exact position or an accurate value for momentum of a
particle. Instead one should think of the probability of finding the particle at a certain
position or of the probable value for the momentum of the particle.

12
Application of Heisenberg Uncertainty principle

Non - existence of electron in the nucleus

We know that from Heisenberg’s uncertainty
h
x . Px  -------------------------- (1)
4
We know that the diameter of the nucleus is of the order of 10–14 m. if suppose the
electron exists inside the nucleus, then uncertainty in its position Δx must not be more than
the size of the nucleus.
i.e., Δx ≤ 10– 14 m
Then, the uncertainty in its momentum is
h 6.625 x 10 34
Px  
4 .x 4 x10 14

Px  0.5 x1020 Ns ----------------------- (2)

We know the energy momentum relation as
E2 = P2c2 + mo2c4 ---------------------- (3)

[ Ref: E = mc2 So E2 = m2c4

m0
P = mv So P2 = m2v2 But m 
2
1 v
c2
We get E2 –P2c2 = mo2c4 ]

Rest mass of electron mo = 9.11 x 10 -31 kg

Substitute all the values of equation (3)
E2 ≥ (0.5 x 10-20 )2 (3 x 108) 2 + (9.11 x 10 -31 )2 x (3 x 108)4
E2 ≥ 1.5 x 10– 12 J
or E ≥ 9.4 MeV

If electron exist inside the nucleus, its energy must be greater than 9.4 MeV. But
the experimental investigation on beta – decay says, the K E of the electron is of the order
of 3 to 4 MeV. This clearly indicates that, electrons cannot exist within the nucleus.

Time independent Schrödinger wave equation

13
 Schrödinger in 1925 developed an equation for the wave associated with the
material particles like electron, proton, neutron, etc. which would describe the behavior of
the particles. He used de Broglie ideas of matter waves.
Consider a system of travelling waves associated with the particle. Let
 ( x, y, z, t ) be the wave function for de – Broglie waves at any time ‘t’. Then the
differential equation for the motion of particle waves is

d 2 d 2 d 2 1 d 2
 2  2  2 . 2  0 ----------------------- (1)
dx 2 dy dz u dt

where ‘u’ is the wave velocity of the particle waves.

The solution of the above equation is

 ( x, y, z, t ) =  o ( x, y, z). e  i  t ---------------- (2)

where  o is the amplitude of particle waves at the point considered.

Differentiate equation (2) twice w. r. to ‘t’ then

d
  o  i  e  i  t
dt
d 2
2
  o  i  (i ) e  i  t
dt
 
= -   o  2 ei  t

= -  2 .  o ( r ) e i  t

d 2
or 2
  2 ------------- (3) [From equ.(2)]
dt
Substituting equation (3) in equation (1) we get

d 2 d 2 d 2  2
 2  2  2 .  0 ------------------ (4)
dx 2 dy dz u

14
 c u
But ω = 2πγ, (Since, γ =  )
 
u
 ω = 2π .

 2
or  then equation (4) becomes
u 
d 2 d 2 d 2 4 2
 2  2  2 .  0 or
dx 2 dy dz 

4 2
 2   0 ---------------- (5)
2
d2 d2 d2
where 2   
dx2 dy 2 dz 2
But from de – Broglie equation
h
 substitute this in equation (5) , we get
P
4 2 P 2
 2   0 -------------- (6)
h2
According to principle of conservation energy
K.E + P.E = Total energy
P2
 V( x , y , z )  E
2m
P2
 ( E  V ) or P 2  2m( E  V )
2m
substituting for P2 in equation (6), we have
8 2 m
 2  ( E  V )  0
h2
substituting    o .e i  t and dividing by e-iωt,

8 2 m
we get  2 o  ( E  V ) o  0 ------------------ (7)
h2
This is time independent Schrödinger equation in 3 dimensions.
In 1 dimension the Schrödinger equation is given by

d 2 o 8 2 m
 2 ( E  V ) o  0 ------------------ (8)
dx 2 h

15
 Physical interpretation of the wave function ( ):

In classical mechanics, I α A2, where I is the intensity of radiation and ‘A’ is the
amplitude of radiation. Similar interpretation is applied to de Broglie waves, associated
with electron or any particle. Hence if we consider a system of electrons and  is the

wave function associated with electron or any particle, then  2 may be regarded as a

measure of density of electrons.

Consider a volume τ, inside which an electron is known
to present, but where exactly the electron is situated inside τ is not
known. If  is the wave function associated with the electron,
then the probability of finding the electron in a certain element

of volume dτ of τ is equal to  d . For this reason  is called the probability function.

2 2

This is the interpretation given by Max Born in 1926.

Normalization of wave function ( ):

Since the electron must be some where inside the volume τ, then the integration of

 over the whole volume τ must be unity, so that

2

 .d  1
2

Above condition is called Normalization of wave function.

Properties of wave function ( ):

The properties of the wave function are

1. ψ is single valued everywhere
2. ψ and its first derivatives with respect to its variables are continuous everywhere.
3. ψ is finite everywhere.

In quantum mechanics it is postulated that the state of a system is completely

characterized by a wave function.

16
Eigen functions and Eigen values

If the wave function ψ for a system is known, then the state of the system can be
determined. A system is defined by its energy, momentum, position etc. In order to find
ψ we have to solve Schrödinger’s equation. Since Schrödinger’s equation is a second
order differential equation, there are several solutions. Among all the solutions we have to
search the wave function which is best acceptable. For an acceptable solution, the wave
function should satisfy the following criteria.

1. ψ is single valued everywhere

2. ψ and its first derivatives with respect to its variables are continuous everywhere.
3. ψ is finite everywhere.

Such acceptable wave functions are named in quantum mechanics as Eigen

functions.

Once Eigen functions are known, by using this in Schrödinger’s equation we can
evaluate energy. Since there is only restricted set of Eigen functions; there is also
restricted set of energy values. These values are called Eigen values (proper or
characteristic values).

Mathematically
(A – λ) ψ= 0 → characteristic equation or eigen equation

λ is Eigen values. “A’ is operator.

Aψ= λψ

d ax
Ex: e  a.e ax
dx

17
Applications of Schrödinger wave equation:

1. Particle in one dimensional potential well of infinite height.

Consider a particle of mass ‘m’ moving freely in the x – direction only in the region
from x = 0 to x = a. Outside this region the potential energy “V’ is taken to be infinite and
within this region it is zero.
Outside the box, the Schrödinger equation is  
d 2 8 2 m
 ( E  )  0 -------------(1) (∵V =  )
dx 2 h2
This equation holds good only if  =0 for all points V=0

outside the box. i.e.,   0 which means that particle

2

cannot be found at all outside the box. -------- (I)

Inside the box, the Schrödinger equation is

d 2 8 2 m
 E  0 -----------------(2) (∵V = 0)
dx 2 h2

 h 2  d 2 
or .   E --------------(3)
8 2 m  dx 2 
This is of the form H = E → Eigen equation

8 2 m
put 2
E  k 2 in equation (2), we get
h
d 2
2
 k 2  0 ----------------------- (4)
dx

Solutions: The solution for the above equation is given by

  C cos kx  D sin kx ---------------------- (5)

But  = 0 at x = 0, as per (I)

∴ Equation (5) → 0 = C cos0 + D sin 0
i.e., C = 0 ----------------- (6)

18
Also  =0 at x = a, as per (I)
Equation (5) → 0 = C cos ka + D sin ka
or D sin ka= 0 (∵ C = 0)
∴ sin Ka = 0 (∵ D ≠ 0)
or ka = nπ
where n = 0,1,2…………….n is called quantum number.
n
∴ k= -----------------(7)
a
substitute the value of ‘C’ and ‘k’ in equation (5), we get

n
 n  D sin x -----------------(8)
a

which represents the permitted solutions.

8 2 m
We know that 2
E  k2
h
k 2h2 n2h2
Or E  ---------------- (9)
8 2 m 8ma 2

In equation (9), the value n = 0 is not acceptable because when n = 0,  n  0 by

equation (8), which means to say that the particle is not present inside the box, which
is not true. Hence the lowest value of n is 1, and the energy corresponding to n =1 is
called zero – point energy, which is given by

h2
E zero po int 
8ma 2

The lowest permitted state of energy is referred to as the ground state energy.
Thus zero point energy is taken as the ground state energy. The states corresponding
to n > 1 are called excited states.

Normalization

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 As we know the particle must present at any time, somewhere inside the box only.
Therefore the integral value of the probability function over the entire space in the box
must be unity.

 .dx  1
2
i.e.,

n
a

D x.dx  1
2
or sin 2
0
a

1  cos 2
Using Sin2θ =
2

D2  2n 
a a
∴  dx   cos x.dx  1
2 0 0
a 

2nx 
a
D2  a
or
2  x  2n sin( a )  1
0

D2  a 
2 a  2n sin( 2n)  0  1

D2a
or 1
2

2
∴ D
a
Thus normalized wave function of a particle in one dimensional box is given by

2  n 
n  . sin  x
a  a 
Wave functions, probability densities and energy levels for particle in a box.

Case (i) n = 1: This is the ground state and the particle is normally found in this state.
For n = 1, Eigen function is
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  
 1  D sin   x
a
Here 1  0 for both x = 0 and x = a
a
But  1 has a maximum value for x = . Thus a plot of  Vs ‘x’ is shown below.
2

Here  1 is the probability density. Fig 1 b indicates the probability of finding the
2

particle at different locations inside the box. Also  1 = 0 for both x = 0 and x = a, it is
2

a
maximum for x = . It means that in ground state, the particle cannot be found at the
2
walls of the box and the probability of finding the particle is maximum at the central
region.

The energy of this state is the ground state energy which is nothing but zero point energy.
h2
E1   E 0 -------------- (11)
8ma 2

Case (ii) n = 2: This is the first excited state. The Eigen function for this state is
2
 2  D sin x
a

a a 3a
Now  2  0, when x = 0, and a. And  2 is maximum for x = and
2 4 4.
a a 3a
Similarly  2 = 0 for x = 0, and a. And  2
2 2
is maximum for x = and
2 4 4.

21
It means that in the first excited state the particle cannot be observed either at the walls or
at the centre.

Energy equation for this state is

h2
E 2  4.  4.E0
8ma 2
Thus the energy in the first excited state is four times the zero point energy.

Case (iii) n = 3: This is second excited state. The Eigen function for this state is
3
 3  D sin x
a
a 2a
Here 3  0 , for x = 0, and and a .
3 3
a a 5a
 3 will be maximum for x = , and .
6 2 6
a a 5a
Similarly  3 is maximum at x =
2
, and .
6 2 6

The energy for this state is given by

E3 = 9 Eo

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2. Free particle

Free particle means, it is not under the influence of any kind of field or force. Thus
it has zero potential. i.e., V = 0. Hence Schrödinger equation becomes

d 2 8 2 m
 2 E  0
dx 2 h

 h 2  d 2 
or    E
8 2 m  dx 2 

Solution for this equation is   C cos kx  D sin k x

Since there are no boundaries, the constants ‘C’, ‘D’ and ‘k’ can now have any values and
‘E’ is given by
k 2h2
E 2
8 m

and ‘E’ is not quantized in this case. Thus when a particle is not bound in a system it does
not have quantized energy states.

---------------- The End ---------------

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