Approved by AICTE, PCI COA, Ministry of HRD, BTEUP, Lucknow, Affiliated to Dr. A.P.J.A.K.

Technical University, Lucknow

Subject Name: Engineering Physics Subject Code- (BAS-101/BAS-201)

UNIT-I, Quantum Mechanics Dr. Amar Pal Singh

Inadequacy Classical Mechanics are:

The inadequacy of Classical Mechanics led to the origin of Quantum mechanics

1. It does not hold in the region of atomic dimensions.
2. It could not explain the observed spectra of black body radiation.
3. The variation of the specific heat of metal and gases is also not explained.
4. It could not explain the observed spectrum of black body radiation.
5. It could not explain the origin of the discrete spectra of atoms. This is so because according
to classical mechanics the energy changes are always continuous.
6. Classical Mechanics could not explain a large number of phenomenon’s. Some of them are
photoelectric effect, Raman Effect, etc.
7. The inadequacy of Classical Mechanics led to the origin of Quantum Mechanics. The
interference, diffraction and polarization phenomena could only be explained by assuming
that light had a wave nature. But some other phenomena, such as black body radiation, the
photoelectric effect and Compton scattering, defied the wave concept of electromagnetic
radiation.

Particle Quality:-
According to the Phenomena of interference, diffraction and Polarization can
only be explained on the basic of wave theory of light. These Phenomena show that Possesses wave
nature. On the other hand the Phenomena show that (Photo electric effect, Compton effect, discrete
emission, and absorption) light Possesses corpuscular (or Particle) nature. Thus we can say that light
Possesses dual nature.
De-Broglie’s of matter wave:-
According to De-Broglie hypothesis, a moving Particle is surrounding
by a wave. The wave length of surrounded wave depends upon the mass of Particle and its velocity.
The wave associated with the Particle is known as matter c.

h h
 
mv p

1
Expression for de-Broglie wavelength:-
According to the Plank’s theory of radiation the energy of a
Photon
hc c
E  hv  … (1) v
 
According to Einstein energy mass relation
E  mc 2 …. (2)
hc
 mc 2
From eq n 1 and 2 

h

mc

If we consider Particle of mass m and velocity v then v  c

h

mv

Different Expressions:-

(a) De-Broglie wavelength In terms of kinetic energy:

1 2 m2v 2 P 2
E mv  
2 2m 2m

P  2mE

h
 
2mE

When a charge Particle carrying a charge q is accelerated by a Potential difference V volts,

the E  qV

h

2mqV

for electron Particle m  9.1 10 31 kg, q  1.6  10 19 c

h  6.625  10 34 Joule-Sec

12.26 0
 A
V
2
 (b) De-Broglie wavelength in terms of Temperature :
When a material Particle in thermal equilibrium at temperature
T then
3
E  kT , K  Boltzmann’s constant  1.38 1023 j / k
2

h h h
   
2mE 3 3mkT
2m  kT
2
(c) De-Broglie wavelength when velocity of Particle is comparable with velocity of light:-
m0
Then the mass of the particle m 
v2
1 2
c
h

mv

v2
h 1 2
 c
m0 v

Properties of Matter waves:-

There are many Properties:-

1. Lighter Particle and smaller velocity, then greater is the wavelength associated with it.
2. When v  0 then   , i.e. wave becomes in terminate and if v   then   0 this shows
that matter waves are generated only when material particles are in motion.
3. The velocity of matter waves depends on the velocity of matter particle, i.e., it is not a
constant while the velocity of electromagnetic is constant.
4. The velocity of matter wave is greater than the velocity of light. This is unexpected result.
We know that E  hv and mc 2
mc2
hv  mc 2  v  c  v
h
mc 2 h c2
Wave velocity u  v   
h mv v

c2
u This is unexpected result.
v

3
 Davisson and Germer Experiment:
The Davisson and Germer experiment
demonstrated the wave nature of the electrons, confirming the earlier hypothesis
of de Broglie. Electrons exhibit diffraction when they are scattered from crystals
whose atoms are spaced appropriately. The apparatus had facility to vary the
energy of the electrons in the primary beam, the angle at which they are incident
upon the target and the position of the detector.

According to the classical physics the scattered electrons should emerge in all directions with
only a moderate dependence of their intensity upon scattering angle and even less upon the
energy of the primary electrons.
During the experiment an accident occurred that allowed air toenter the apparatus and oxidize
the metal surface. To reduce the oxide to pure nickel the target was baked in hightemperature
oven. After heating the target was returned tothe apparatus and measurements resumed.
Surprisingly, instead of a continuous variation of scattered electron intensity with angle distinct
maxima and minimawere observed whose position depended on the electronenergy.

The polar graph of electrons intensity

The method of plotting is such that the intensity at an angle is proportional to the
distance of the curve at that angle from the point of scattering two questions

4
Phase velocity or wave velocity:-
When a monochromatic wave i.e. a wave of single frequency and
wavelength, travels through a medium its velocity of advancement in the medium is called as wave
velocity consider a wave whose displacement y is
y  a sin wt  kx
Where a is the amplitude, w is angular frequency w  2
2
K is the propagation constant of the wave for the wave wt  kx is the phase of wave

motion for the planes of constant phase wt  kx  constant
Differentiate with respect to t.
kdx
w 0
dt

dx w
  vp v p is called phase velocity.
dt k

Group Velocity:-
The velocity with which a wave packet moves forward in the medium is
called group velocity denoted by v g .
Let us consider the case of two wave trains having same amplitude and different angular
velocity w1 and w2 , k1 and k2 are propagation constant.
y1  a sin w1t  k1 x, y2  a sin w2 t  k 2 x
Apply Superposition Principal
y  y1  y2  a sin w1t  k1 x  a sin w2t  k2 x

A B A B
sin A  sin B  2 sin cos
2 2

 w  w2 t k1  k 2 x   w  w2 t k1  k 2 x 
y  2a sin  1   cos  1  
 2 2   2 2

 w  w2 t k1  k 2 x   w1  w2 t k1  k 2 x 

y  2a cos  1   sin   
 2 2 2 2

 w  w2 t k1  k 2 x 
y  A sin  1  
 2 2 
 w  w2 t k1  k 2 x 
where A  2a cos  1   is the modified amplitude of the wave Packet in space
 2 2 
and time.

5
  w k  w1  w2  w
y  2a cos  t x sin wt  kx Where
 2 2  k1  k 2  k
w  w2 w
vg  1  
k1  k 2 k

w w1  w2
vg  is called group velocity w
k 2
k1  k 2
k
2
Relation between Group velocity and Phase Velocity:-
w
We know the wave velocity u p   w  kvp
k
Differentiation with respect to k

group velocity v g 
dw d
 kvp   v p  k dv p
dk dk dk
2
Where K  where  is wavelength

2
dk   .d
2
2 d vp
vg  v p 
  2 
  2 d 
  
d vp
vg  v p  
d

In dispersive medium in which the wave velocity is frequency dependent in this medium
  
group velocity v g  is less than wave velocity v p . vg u p the velocity is independent of frequency
2

dv p
that is v p is constant therefore  0 in non dispersive medium or free space v g  v p the
d
group velocity of a wave packet is equal to wave velocity.

Relation between Wave (Phase) velocity of De-Broglie wave:-

h
According to De-Broglie wave   … (1) where h is plank
mv
constant
2 2mv
Propagation constant of the wave k   …. (2)
 h
E 2E
Energy of the Particle E  hv or v  and w  2v 
h h

6
Einstein’s mass energy relation E  mc 2

Divide equation (3) an (4)

2 mc 2
w …. (3)
h
w 2 mc 2 c 2
vp     vg  v
k h v
2 mv
h
2
c
 vg v p  c
2
: vp 
vg
The phase velocity of de-Broglie wave v p is greater than the velocity of light c. this is
contradictory result. Or unexpected result

Relation between group velocity of De-Broglie’s waves:-

Suppose a particle of rest mass m0 is moving with velocity v its total energy and momentum
m0 c 2 m0 v
E  mc2  and P  mv 
v2 v2
1 1
c2 c2
E  hv
Angular frequency w  2v or E
v
h
2E 2 m0 c 2
w  …. (1)
h v2
h 1 2
c
Differentiation with respect to v

3

dw 2 m0 c 2 d   v  2  2 m0 c 2  1  v 2   2v 
1 2

 1        1  2    2 
dv h dv   c   h  2  c   c 
dw 2 m0 v
 3 …. (2)
dv  v2 
2

h1  2 
 c 
2 2 mv 2 m0 v
Propagation constant k   

1
h  v2 
2

h1  2 
 c 

7
Differentiation with respect to v
dk 2 m0 d   v 2  
1
2

 , v1  2  
dv h dv   c  


2m0   1   v 2   2v   v 2  
3 1
2 2

 v   1  2    2   1  2  
h   2  c   c   c  

3

2 m0  v 2   v 2 v2 
2

 1     1  2 
h  c2  c2 c 
dk 2 m0
 3
….(3)
dv  v2 
2

h1  2 
 c 
dw dw dw
Divided (2)/(3) vg    v
dk dk dk
dk
dv
v g  v Hence group velocity is equal to the velocity of the particle with which the
waves are traveling.
BORN INTERPRETATION OF THE WAVE FUNCTION AND ITS SIGNIFICANCE Or
Wave function 
The wave function gives the information about the particle within the wave Packet. It is
denoted by Symbol  . Wave function  follows three conditions.
Matter waves are represented by a complex function, Ψ (x,t), which is called a wave function. The
wave function is not directly associated with any physical quantity but the square of the wave
function
represents the probability density in a given region. The wave function should satisfy the following
conditions:
(i) Ψ should be finite
(ii) Ψ should be single valued
(iii) Ψ and its first derivative should be continuous
(iv) Ψ should be normalizable,
 x   = 1 Where V = volume in which the particle is expected to be found
2

Probability:-
According scientist max born  x  
2
gives the probability of finding the particle in the
state  .

P    n nx dV dV  dx dy dz


8
 
P    n dx
2
For one dimensional



  n dx 1
2
Condition for Normalization



Expectation value  x    n x  nx dx


 x   x n dx
2


Equation of Motion of Matter waves:-

There are two types.
(i) Schrodinger Time independent wave equation:-
(ii) Schrodinger Time dependent wave equation:

(i) Schrodinger Time independent wave equation:-

According to De-Broglie theory, a
h
Particle of mass m is always associated with a wave whose wavelength is given by   ,
mv
consider a system of stationary waves associated with a particle. Let x, y, z be the coordinates of
the particle and  be the wave function.
According to classical the wave equation is for wave optics.

 2  2  2 1  2
  
x 2 y 2 z 2 c 2 t 2
According to Quantum mechanics put v= c and ϕ = ψ

 2  2  2 1  2
  
x 2 y 2 z 2 v 2 t 2

2 2 2
Where v is the velocity of the particle 2    for Laplacian Operator
x 2 y 2 z
1  2
 2 
v 2 t 2
 2
v 2  2  ….. (1)
t 2
The solution of this equation is
w  2v
   0 sin wt   0 sin 2vt …. (2)
where v is frequency

9
 Differentiating eq n 2 Differentiation with respect to (t)

  0 cos 2vt2v 
t
Again Differentiation with respect to (t)

 2
  0 sin 2vt2v 
2

t 2

 2 4 2 v 2 v
 4 v   
2 2
…. (3) v
t 2 2 
From (1) and (3) equation
4 2 v 2 4 2
v  
2 2
 2
 0
2 2
h
According to De-Broglie  
mv

4 2 m 2 v 2
 2   0 …. (4)
h2
1 2
E and U be the to total and Potential energy E  mv  U
2

mv  E  U  m 2 v 2  2mE  U ) 
1 2
2
Put in m v value in eq n 4
2 2

8 2 m
 2  E  U   0.....(5)
h2

for free Particle potential energy ( U  0 )

8 2 mE
 2   0
h2
ℎ
In terms of h = put value in equation (5)
2𝜋

 2 
2m
E  U   0
h2

This is Schrodinger time independent wave equation.

10
Schrodinger time dependent wave equation:-
The Schrödinger time dependent wave equation
may be obtained from Schrödinger time independent wave equation. The differential equation
represent a one – dimensional wave motion is
 2
 v 2 2 …. (1)
t 2
The solution of this equation is
   0 e iwt …. ( 2)
Differentiating eq . 2 Differentiation with respect to (t)
n


  0 e iwt  iw 
t

w  2v
 iw 
 i 2v E  hv
h
E
 i 2  h
h (3) 2
Multiply and divide by i equation (3)
 i2E
 
ih i2 = -1
 E

t ih

E  i h
t
According to Schrödinger time in-dependent wave equation
 2  2 E  V   0
2m
h
 2  2 E  V   0
2m
…. (3)
h
Put the value E in equation (3)
2m   
 2  2 
ih  V   0
h  t 
2m   
 2   2 
ih  V   0
h  t 
h2 2 
    ih  U
2m t
h2 2 
  ih
2m t
This equation is called Schrödinger time dependent wave equation
11
Particle in one-Dimensional Box or Infinite Potential Well:-
Let us consider a particle of mass m
moving along x  axis between the two rigid walls A and B at x  0 x  L , Particle is free to
move between the walls.

Suppose that the potential energy V of the particle is zero inside the box, but becomes infinite at the
walls at outside that is,
U  0 For 0  x  L
U   For 0  x and x  L
Under these conditions, particle is said is move in an infinitely deep potential well or in an
infinite square well.
According to Schrödinger equation for free particle within the box
U 0
d 2 8 2 m.E
Then Schrödinger equation  0 … (1)
dx 2 h2
8 2 mE
Suppose k 2  …. (2)
h2
d 2
 k 2  0 …. (3)
dx 2
The general solution of differential eq n
  A sin kx  B cos kx …. (4)
Where A and B are constant
Apply boundary conditions, as the particle cannot have infinite energy in neither penetrate the
walls nor exist outside the box. That is   0 at x  0 and x  L
Apply first boundary condition,   0 at x  0 at eq n 4
0  Asin 0  B cos 0
B0
  Asin kx (5)
Apply second boundary condition   0 at x  L
Asin kL  0

sin kL  sin n n  1, 2, 3
12
n  0 is not possible because it gives   0 , everywhere, it means that the particle is nowhere inside
the box which is impossible kL  n
n
K n  1, 2, 3
L
n 2 2
k2  …. (6)
L2
8 2 mE n 2 2
From (2) and (6) equation 
h2 L2
n2h2
En 
8mL2
The particle cannot an arbitrary energy, but can have only certain discrete energy
corresponding energy to n  1, 2, 3

Normalized wave function:-

n
We know wave function   Asin kx K
L
nx
 n  A sin
L

  n dx 1
2
Apply normalized condition


nx
2



A sin
L
dx  1

L nx
 0
A 2 sin 2
L
dx  1

A2  cos 2nx 

L
1  L 
dx  1
2 0

L
 
 

A2  2nx 
x 1
2  L 
 2nx 
 
 L 0
A2 2
L 1  A 
2 L

2 nx
n  sin
L L

13
The first three normalized wave function  1 ,  2 ,  3 at on with corresponding probability
1 ,  2 , 3 of particle in a box according to fig. It is clear  n may be possible or negative
2 2 3

but  n
2
is always positive.

Black Body:-
A black body is a body that absorbs completely all electromagnetic radiation, of all
wave length incident upon it. It appears black when it is cold. The terms block body was
introduced by Kirchhoff. He told us that a block body not only completely absorbs all the radiation
falling on it, but also behaves as perfect radiation and emits all the radiations when heated to a
suitable high temp.
A perfect black body does not exist in nature and can not be realized in practice. Fery’ has
devised a black body which approximates very closely to the properties of a perfect black body.

14
Stefan’s Law:-
When a black body is heated, it emits radiations of all possible wave lengths. Stefan’s gave
the law for energy distribution among the different wave length. According to it, the total amount
of radiant energy by a black body per unit area per second due to all wave length is directly
proportional to fourth power of absolute temp.
i.e. E  T 4 or E  T
4

Where   5.67 10 8 w m 2 k 4 is known as Stefan’s constant.

Limitations of Classical theory:-

Many Scientists developed different formula to explain the distribution of energy among the
wavelengths on the basis of classical theory but none was able to explain the entire spectrum.

(i) Wien’s Displacement Law:-

Wien’s Law on the basis of his work on the distribution of energy
among the different wavelengths at various temperatures of a block body showed that the peak in
the black body spectrum shifts to progressively shorter wavelengths as the temperatures increased.
i.e. “In the black body spectrum, the wavelengths m  , for which emissive power is maximum, is
power is maximum, is inversely proportional to the obsolete temp. T of the body”, i.e.
1
m 
T
or

m T  Constant

When also showed that the energy emitted at the wavelength of maximum emission, is
proportional to the fifth power of absolute temperature of the black body.
i.e. Em  T 5
Em  T 5  Constant

Rayleigh – Jeans Law :-

According to electromagnetic theory, a black body radiator emits radiation
of continuously variable wavelengths from zero to infinity. This radiation assumed as broken up into
independent mode of vibrations. Number f these mode f vibration is calculated by statistical
mechanics. The energy carried by each mode of vibration is
8kT
E  4

Where K is the Boltzmann’s constant.

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Compton Effect:
A. H. Compton observed that “when a monochromatic beam of high frequency
(lower wavelength) radiation (e.g., X-rays and γ-ray) is scattered by a substance, the scattered
radiation contains two type of wavelengths one having same wavelength as that of incident radiation
while the other having the wavelength greater (or lower frequency) than that of incident
radiations. This effect is known as Compton Effect.
Quantum Explanation: The explanation was given by Compton which was based on quantum
theory of light. According to quantum theory when photon of energy hυ strikes with the substance
some of the energy of photon is transferred to the electrons, therefore the energy (or frequency) of
photon reduces and wavelength increases.
Various assumptions were made for explaining the effect these were
(i) Compton Effect is the result of interaction of an individual particle and free electron of target.
(ii) The collision is relativistic and elastic.
(iii) The laws of conservation of energy and momentum hold good.

The energy of the system before collision

The energy of the system after collision

According to the principle of conservation of energy

(1)

(2)

According to the principle of conservation of linear momentum along and perpendicular to the
direction of incident photon (i.e., along x and y axis), we have

For X-Axis

(3)

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For Y-Axis (4)

Solving equation (3) & (4)

(5)

(6)

Squaring and adding, equation (5) & (6) we get

(7)

Squaring equation (2) on both side

(8)

Subtracting equation (8) - (7) we get

(9)

According to the theory of relativity

Multiplying both sides by c2, we get

(10)

Put value in equation (9) then

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 .

To find the relation in term of wavelength, let us substitute and, we thus

have

1. The wavelength of the scattered photon λ’ is greater than the wavelength of incident photon λ.

2. ∆ λ is independent of the incident wavelength.

3. ∆ λ have the same value for all substance containing free electron

4. ∆ λ only depend on the scattering angle .

1. when = 0; cos =1

∆ λ = λ’ – λ = 0

λ’ = λ, the scattered wavelength is same as the incident wavelength in the direction of

incidence.

2. when =90 o ; cosϕ =0

Where λc is called the Compton wavelength of the electron.

3. when =180 o ; cos = -1

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 4. Why Compton Effect is not observed in visible spectrum
o o
The maximum change in wavelength max is 0.04652 A or roughly 0.05 A . This small therefore
can not be observed for wavelength longer than few angstrom units. For example-

For X-ray, the incident radiation is about 1Ao , max is 0.05 Aotherefore the percentage of incident
radiation is about 5%(detectable)

For Visible radiation, the incident radiation is about 5000 Ao, max is 0.05 Ao therefore the
percentage of incident radiation is about 0.001% (undetectable

Direction of Recoil electron:

Dividing equation (6) by (5) direction of recoil electron is given by

Where

Kinetic Energy of Recoil Electron

The kinetic energy gained by electron is equal to the energy loss by the scattered
photon

Where

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