QUANTUM MECHANICS

Inadequacy of classical mechanics & Need of quantum Mechanics:

 Towards the end of ninetieth century, classical physics had attended near perfection
and tremendous success both in theoretical and experimental fronts.
Almost all the physical phenomena ranging from the dynamics of the point particles
rigid bodies, thermodynamics, geometrical and wave optics, electromagnetism and
other related facts could be described in the frame work of classical mechanics.
The backbones of classical mechanics were:
1. Newtonian Mechanics
2. Laws of thermodynamics
3. Fresnel wave theory
4. Maxwell’s theory of electromagnetism etc.
The fundamental ingredients in classical physics were:
1. The classical physics is deterministic in nature i. e. given the relevant laws, the
behavior of the system can exactly be predicted. Further, physical quantities can
in principle be measured with unlimited accuracy.
2. The various physical quantities and their changes can have any continuous value
without restriction.
3. Particles and waves in classical physics are regarded as distinct and separate
entities
 QUANTUM MECHANICS
The above ideas though were in numerous success in explaining the phenomena
Involving macroscopic bodies, yet became inadequate to account for many
experimental observations made during late ninetieth century and early twentieth
Century.

Some of the observations which classical physics could not explain are:
1. Energy distribution in spectrum of blackbody radiation
2. Photoelectric effect
3. Compton effect
4. Atomic spectra and structure of atoms
5. Variation of specific heat of solids with temperature in low temp region
Black body radiation spectrum:
 All normal matter absorbs electromagnetic radiation to some degree.
 An object that absorbs all radiation falling on it, at all wavelengths, is called a
black body. When a black body is at a uniform temperature, its emission (emissivity
or emission intensity) has a characteristic frequency distribution that depends of
temp.
A perfectly insulated enclosure that is in thermal equilibrium internally contains
black-body radiation and will emit it through a hole made in its wall, provided the
hole is small enough to have negligible effect upon the equilibrium.
 QUANTUM MECHANICS
Characteristics of Blackbody radiation:
1. For a given temperature, the energy density (and hence emissive power) at low
frequencies and high frequencies is small. It steadily increases with frequency, till
it attains a maximum and then again decreases to zero.
2. The total energy density per unit volume/the total emission from unit area in one
second (emissivity) is directly proportional to fourth power of temperature.
E  T 4  T 4 (  5.67 108Watt / m2 K 4 )        (1)
3. Corresponding to a particular frequency, the emissive power is more at high
temperature
4. The frequency corresponding to
maximum emission is proportional
to temperature
mT  const.  2.898 10 3 mK  (2)
(Wein ' sDisplacementlaw).
From thermodynamic considerations,
Expressions (1) and (2) could successfully
Be derived. Then, the main task
remained was to give a theoretical
explanation to the variation of u ~ 
that should agrees well with the experimental observations.
 QUANTUM MECHANICS
Wien's distribution Law: 
b

In 1986, Wien gave an empirical law: u ( )d  a e d      (3)

3 kT

Where, ‘a’ and ‘b’ are constants independent of T and ν.

Wien’s distribution formula (3) agreed well with experiment for high frequencies
(i.e. low wavelengths) but was in violent disagreement for low frequencies (i. e. at
High wavelengths)
 QUANTUM MECHANICS
Rayleigh-Jean’s law:
Applying statistical mechanics and thermodynamics, Rayleigh-Jean derived the
Distribution law as: u ( )d  83 kTd      (4)
2

From Rayleigh-Jean’s law, u( )  2 . So u ( ) diverges at high frequencies. But

experiments shows that, u( )  0 as   0 . This discrepancy is known as “Ultraviolet
Catastrophe”, because the divergence increases towards the high frequency end (i. e.
Ultraviolet end) of the spectrum.
Plank’s Quantum Idea of Radiation and Plank’s Radiation Formula:
In 1900, through his revolutionary hypothesis, Plank derived his expression for spectral
energy density. Following were Plank’s hypothesis:
1. A radiation chamber in equilibrium is filled with atom like oscillators (oscillating
with different frequencies)which continuously exchange energy with blackbody
radiation in a discrete fashion.
2. The energy of these oscillators is quantized. If the oscillator has frequency  , the
energy of the oscillator is restricted to one of the values  n  nh , where, n  0,1,2...
and h is the plank’s constant.
3. The atomic oscillators cannot exchange energy with radiation in a continuous
manner, but in discrete amount (called as quantum of energy) of value h .
 QUANTUM MECHANICS
Using the above mentioned revolutionary ideas, Plank derived the spectral energy
Distribution formula: 3
8h 1
u ( )d  h
d      (5)
c3
e kT
1
c
Using   , we can write eqn (5) as:

8hc 1
u ( )d  d      (6)
5 hc
e kT
1
Expressions (5) and (6) successfully agreed with experimental observations.
Expressions (1) and (2) also could be derived from expression (5) and (6).

Note: This quantum idea of energy of an oscillator and exchange of energy of oscillator
with radiation also successfully explained the low temperature behavior of molar
specific heat of solids. With further extension of this quantum idea to the
propagation of energy with electromagnetic radiation successfully explained some
other phenomena in other domain of physics which could otherwise be explained
by classical ideas.
Question: Name four experimental observations which classical physics failed
to explain.
 QUANTUM MECHANICS
PHOTO-ELECTRIC EFFECT:
“The phenomena of ejection of electrons from the surface of metals when light of
suitable frequency is incident on it is called as Photoelectric effect.”
Lenard and Hallwalk extensively studied the photoelectric effect. Their observations
can be summarized as follows.
1. Photoelectric effect is an instantaneous process.
2. At a constant intensity and frequency of
light, the photocurrent at first
increases and then attains a
constant value (Called as
Saturation current). This
saturation current increases
linearly with increase in intensity of
incident light(keeping frequency const.)
3. When the potential of anode is made
negative w. r. t. cathode, the current
decrease steadily and becomes zero
at a potential called as stopping
potential (V0) (Stopping potential is
proportional to maximum K. E. of emitted electrons)
 QUANTUM MECHANICS
4. The stopping potential and hence the maximum
K. E. of emitted electrons is independent of intensity.

5. The stopping potential increased linearly

with increase in frequency. For same frequency,
the stopping potential is different for different
metals (i. e. with different work function ‘φ’)
 QUANTUM MECHANICS
6. For each photoelectric material, there exists
a minimum frequency (Called as threshold
Frequency(f0)), below which no photoelectrons
are emitted, however large the intensity of
incident light may be.
The above noted observations are sometimes
Called as laws of photoelectric effect.
Einstein’s explanation:
Einstein explained the above observations with
extension to plank’s idea.
He postulated that:
1. Radiation energy is built up of discrete units or localized bundles of electromagnetic
energy, called as photons which move with velocity of light and has zero rest mass.
2. Each photon (i.e. the quantum of energy) has energy h (where ‘h’ is the plank’s
constant ) and is independent of intensity of light.
3. The intensity at a given frequency is determined by the no of photons incident per
second. Hence incraese in intensity increases the no of photons incidented per sec
but individual photon energy remains unaffected.
 QUANTUM MECHANICS
With the above postulates for radiations, Einstein assumed that, when a photon
incidents on an electron near to surface, the electron absorbs the photon and gains
Energy ‘hν’. If this quantum of energy exceeds the minimum energy needed for
Electron to escape from metal surface (i. e. work function φ), then the electron emits
From the metal and the excess energy ‘hν – φ’ appears as the kinetic energy of the
Electron. Hence the equation for photoelectric emission becomes:
1 (Where V0 is the stopping
h    mvmax  eV0    (7)
2

2 potential)

This equation explains all important features of photoelectric effect which could not
Be explained by classical physics.
This eqn (7) is called as Einstein’s Photoelectric equation.
This equation can also be written as:
h 
V0          (8)
e e
Hence, ‘V0 ‘ vs ‘ν’ graph should be a straight line, whose slope is equal to ‘h/e’.
From the knowledge of slope and y-intercept one can calculate the plank’s constant
And work function of metal
 QUANTUM MECHANICS
Particle nature of Radiation:
We can summarise the photon picture of electromagnetic radiation as:
1. In interaction of radiation with matter, radiation behaves as if it is made up of
particles called photons.
2. Each photon has an energy ‘hν’ and speed ‘c’, (in vaccum)the speed of light.
3. All photons of radiation of a particular frequency/wavelength have same energy
‘hν=hc/λ’, whatever the intensity of radiation may be. Photon energy is dependent
on frequency and independent of intensity.
4. Photons are electrically neutral and are not deflected by electric or magnetic field.
5. If a photon has mass ‘m’, then from theory of relativity, its energy is:
m0 c 2
E  mc 
2
1/ 2
   (9) where, m0 is rest mass of photon.
 v2 
1  2 
 c 
Since photon moves with speed of light, so ‘v=c’. If m0c2≠0, then ‘E’ will become
infinite. But ‘E’ of photon is finite (= hν).. Hence, photon has zero rest mass.
6. Momentum of photon:
Taking photon as a particle, it has momentum also.
From relativity,E  p 2c 2  m0 2c 4  (10)
Since photon has zero rest mass, so E  pc  p  E
c
 QUANTUM MECHANICS
E h h
Since E  h  hc
, sop      (11)
 c c 
The direction of photon momentum is in the direction of radiation.
7. In a photo-particle collision(say photon-electron collision), the total energy and
momentum are conserved. However, the no of photons may not be conserved.
The photon may be absorbed or photon may be created.
Examples:
1. What is the energy in electron volt of a photon of wavelength 1Å? What is its
momentum?
2. Calculate the number of photons emitted per second by a 100 watt sodium lamp.
{λ=5893Å for sodium}
3. What is the wavelength of photon whose energy is equal to rest energy of an
electron.
4. The energy of a photon is 5.6 eV. Find its momentum.
5. What is the frequency of an X-ray photon whose momentum is
1.1×10-23 kg.m/sec?
6. How much energy must a photon have if it is to have the momentum of a
100 MeV proton?
 QUANTUM MECHANICS
Dual Nature of Radiation:
The successful explanation of many experimentally observed phenomenas like
Photoelectric effect, Compton effect etc., by treating radiation as stream of particles
called photons, convincingly demonstrated the particle nature of light.
On the other hand, phenomena like interference, diffraction and polarization etc
provide sufficient evidence for wave nature of radiation. The wave characteristics like
frequency and wavelength of light wave are related to the particle characteristics like
Energy and linear momentum of photon.
Thus, radiation behaves as waves in some situations and particles in some other
situations. However, both the wave and particle characteristics are not exhibited in
same observation.

WAVE NATURE OF PARTICLES (MATTER WAVES AND DEBROGLIE HYPOTHESIS

In 1923, a young Frenchman, Louis-Victor DE Broglie, a graduate student in physics
Suggested that, “the wave particle duality is a universal principle and is not restircted
Only to electromagnetic radiations”. He argued that, “since nature is symmetric, what
Is true for photons (radiations) must be true true for material particles”. Hence
Material particles must exibit wave like properties.
 QUANTUM MECHANICS
De Broglie proposed that, all material particles can manifest themselves as waves
Called as matter waves (also called as De Broglie waves). The wavelength of mater
Waves associated with a moving particle of linear momentum ‘p=mv’ is given by:
h
      (12)
p
De Broglie assumed that, the role of matter waves in guiding the motion of material
Particles is analogous to that of electromagnetic waves in guiding the motion of photons.
For non-relativistic particles:( when (v  c) )
(i) When v<<c, mass in motion ‘m’=rest mass ‘m0’.
h
So p = m0v. Hence,  
m0 v
(ii) For a non relativistic free particle (a particle is said to be free particle, if no force
acts on it), the total energy (E) is equal to its kinetic energy (K).
Then, h h
p2          (13)
K  p  2mK  2mE , So 2 mK 2 mE
2m
(iii) If a particle is accelerated through a potential difference of ‘V’ volt, then K. E.
2
p h
gained is K  2m  qV  p  2mqV So        (14)
2mqV
For an electron: m  m  9.11031 kg
e

q  e  1.6 1019 C
1.227
Hence: e  nm
V
 QUANTUM MECHANICS
(iv) In case the particle is in a potential field possessing potential energy ‘U’, the
kinetic energy is given by: K = (E-U). So p  2m( E  V )
h
Then       (15)
2 m( E  U )

(v) The average kinetic energy of a gas molecule (having three degrees of freedom)
in an ideal gas is given by: p2 3
K  kT
2m 2
So   h
   (16)
3mkT
For relativistic particles:( when v ~ c )
(i) For relativistic particles mass of the body changes with speed according to relatio
m0
m 1/ 2
     (17)
 v 2

1  2 
 c 
m0 v h h
p  mv           (18)
So  v 
2 1/ 2 Hence mv m0 v
1  2   v2 
1/ 2

 c  1  2 
 c  h hc
     (20)
E 2  m0 c 4
2
(ii) Also So E  m0 c E  m0 c
2 2 4 2 2 4
E  p c  m0 c  p       (19)
2 2 2 4

c c
 QUANTUM MECHANICS
How to distinguish between relativistic and non relativistic case:
(i) Check whether v  c (non relativistic case) or v ~ c (relativistic case)
(ii) In expression, E  p 2c 2  m0 2c 4 , m c is the rest energy of the particle. So kinetic
0
2

energy of the particle in relativistic case is given by:

K  E  m0c 2    (21)
This kinetic energy is also proportional to pc value. If pc value is negligible to
m0 c 2 , then motion is non relativistic. But if they are comparable, then
consideration should be relativistic.
Example:
Calculate the De Broglie wavelength of :
(i) An electron moving at 300 m/s.
(ii) A 10 gm particle moving at 2 m/s.
(iii) A proton having K.E. 40 eV.
(iv) An electron having K. E. 3 GeV.
(v) An oil drop of mass 0.002 gm and carrying two unit electronic excess charge is
accelerated through a potential difference of 30 V.
(vI) A thermal neutron at 270C.
Note: In example (ii), you can mark that the De Broglie wavelength is very small in
comparision to the dimension of the body, hence we wouldnot expect to find any wave
aspect in its behavior.
 QUANTUM MECHANICS
Example:
Find the kinetic energy of a propton whose de-broglie wavelength is 1 femtometer.
Ans:
Given   10 m so, pc   c  1.241GeV
15 h

Rest energy of proton is : E0  m0c 2  0.938GeV

So pc is comparable to m0c 2 . Hence, the relativistic case is to be used.
The total energy of the proton is:
E  m0 c 4  p 2c 2  E0  p 2c 2  1.555GeV
2 2

Hence K. E. is: K  E  E0  1.555GeV  0.938GeV  0.617GeV

Assignments:
1. Distinguish between electromagnetic waves and de-Broglie waves.
2. Calculate the debroglie wavelength of an electron moving with a speed of
(i) 1000m/s (ii) 0.8c.
3. Assuming the inner core temperature of sun to be , find the debroglie wavelength of
a proton in the core.
4. Calculate the de-broglie wavelength of a neutron of energy 1MeV.
5. If a photon has a wavelength equal to the de broglie wavelength of the electron
Moving with speed 10 km/s, what is the photon’s energy?
 QUANTUM MECHANICS
6. An electron and a proton has same de-Broglie wavelength. Compare their K. E.
7. An electron initially at rest is accelerated across a potential difference of 3 keV. What
are its wavelength, momentum, kinetic energy and total energy?
8. Find the kinetic energy of (a) photons, (b) electrons, (b) neutrons, and α-particles
that have a de-broglie wavelength of 0.15 nm.
9. What is the wavelength of an electron with kinetic energy (a) 40 eV and (b) 4.6 MeV?
10. What is the K. E. of an electron whose de-broglie wavelength is (i)1.6 Å and (ii) 2 fm
11. What is the wavelength of an electron whose K.E. is (i) 5 eV and (ii) 0.5 MeV
 QUANTUM MECHANICS
Phase Velocity of a Monochromatic wave:
The speed with which the surface of constant  
phase in a progressive wave moves is called as
phase velocity.
For a one dimensional sinusoidal wave,   A sin( wt  kx   )
let the phase at ‘x’ at ‘t’ found to have travelled to ‘x+dx’ at ‘t+dt’. Then:
kx  wt      k ( x  dx)  w(t  dt )  
dx w
 kdx  wdt  0    f
dt k
w
 phasevelocity  v p   f      (23)
k
Phase velocity of De-Broglie waves and velocity paradox:
As per De Broglie, the matter wave representing a particle moving with momentum ‘p’
Is   h / p. As a particle can not have two momentum at same instant and as in classica
Physics, momentum can be measured exactly, hence λ has a fixed value (i. e. matter
Wave representing the particle is a monochromatic wave). Then velocity of matter
Wave is given by its phase velocity:
w
vp   f
k
 QUANTUM MECHANICS
h h h / 2 h 2
For De broglie waves:   p  p     / 2 
2 
 k      (24)

h
And E  h  2        (25)
2
Hence phase velocity of De Broglie waves is:
w  E
vp         (26)
k k p
Case 1: For non relativistic free particle, p2 E p mv v
E    
2m p 2m 2m 2
E v
 vp        (27)
p 2
So in non relativistic limit, phase velocity of matter waves is equal to half of the particle
velocity . m0 v
m c 2 p  mv 
Case 2: For relativistic free particle, E  mc 2  0 1
1 and  v 2
2

 v2 2 
1  c 2 

1  2   
 c 
E c2
 v p        (28)
p v

The velocity of material particles is always less than ‘c’. So the phase velocity of matter
Waves must be greater than ‘c’.
 QUANTUM MECHANICS
The above discussion shows that, in both relativistic and non relativistic motion, the
velocity of the particle is different from the phase velocity of the De Broglie wave that
Represents it. In non relativistic motion, the particle leaves behind the phase, whereas
In relativistic motion, the phase leaves behind the particle. This puzzling disagreement
Is referred to as “velocity paradox of matter waves”
It is a dire necessity that the wave (that represents the particle) and the particle must
Move with same velocity.
In our attempt to represent particles by plane waves of the type given by   A sin( wt  kx   )
We have encountered the velocity paradox. The resulting phase velocity does not agree
with the particle velocity. In fact, a particle is a localized object, whereas a plane wave
is an infinitely extended entity having no distinguishing marks to represent the location
of the particle. This localization can be achieved by modulating the wave to form a
wave group or a wave packet. This modulation can be achieved by superposing large no
of waves. The wave packet or the entire group of wave travels with velocity called as
Group velocity (vg ), which would correspond to the particle velocity. The individual
waves which comprise the wavepacket would travel with the phase velocity (vp ).
 QUANTUM MECHANICS
Formation of wave packet (Group velocity):
Actually a material particle is represented by a wave packet which is formed due to
superposition of large no of waves of slightly different wavelength and frequency.
Here we attempt to construct a wave packet by adding two wave functions  1 ( x, t )
and  2 ( x, t ) having same amplitude but slightly differing wavelength and frequencies.
Let  1 ( x, t ) and  2 ( x, t ) are given by:
 1 ( x, t )  a sin( wt  kx)
and  2 ( x, t )  a sin( w' t  k ' x) where, w'  w  w and k '  k  k
The resultant wave after superposition of these two waves is:
 ( x, t )   1 ( x , t )   2 ( x, t )
  ( x, t )  asin wt  kx  sin{w  wt  k  k x}
 wt  ( w  w)t kx  (k  k ) x   w k 
  ( x, t )  2a sin    cos  2 t  x
 2 2 2 
 w k   w   k 
   x, t   2a cos  t x  sin  w  t   k  x       ( 29)
 2 2   2   2 
 w   k   w k 
  ( x, t )  A sin  w  t   k  x  Where A  2a cos  t x       (30)
 2   2   2 2 
 QUANTUM MECHANICS
Expression (29) represents a wave of amplitude A given by expression (30). The
amplitude ‘A’ is modulated by another wave of angular frequency Δw/2 and wave
Number Δk/2. This modulation results successive wave groups which will be seen
progressing with time with a velocity called as group velocity (vg ).
 QUANTUM MECHANICS
The velocity with which a group moves is equal to the velocity with which a particular
Amplitude proceeds with time.
From expression (30), if the amplitude of group is ‘A’ at ‘x’ at ‘t’ and the same amplitude
is observed at a later position ‘x+dx’ at a later instant ‘t+dt’, then:
 w k   w   k  
2a cos  t x   2a cos   (t  dt )    ( x  dx ) 
 2 2   2   2  
w k  w   k 
 t x (t  dt )   ( x  dx )
2 2  2   2 
w k
 dt  dx  0
2 2
dx w dw
   ( with k  0)
dt k dk
dx
But dt
is the velocity with which the group of wave moves.

So group velocity is:

dw
vg       (31)
dk
 QUANTUM MECHANICS
Relation between group velocity and phase velocity:
dw
Group velocity of a wave packet is: vg 
dk
w
Phase velocity of a component wave (monochromatic wave) is: vp 
k
From expression of phase velocity: w  v p k
Differentiating both sides with respect to ‘k’, we get:
dw dv p
 vp  k      (32)
dk dk
dv p d
 vg  v p  k 
d dk
But   2  d   2
2
k dk k
2 dv p 2 dv p
So vg  v p  k  2  vp 
k d k d
dv p
 vg  v p        (33)
d
Expression (33) gives the relation between group velocity and phase velocity.
 QUANTUM MECHANICS
A dispersive medium is one in which the phase velocity is a function of wavelength.
In a non dispersive medium: dv p
0
d
Hence vg  v p . So for a non dispersive medium, phase velocity and group velocity
are same.
Group velocity of De Broglie waves:
For De Broglie waves, E  w and p  k
So group velocity of De Broglie waves is given by:
dw dw d (w) dE
vg    
dk dk d (k ) dk
dE
 vg       (34)
dk
Phase and Group velocity of photons:
For photons, E  pc  E  c  v  c
p
p
dE
Also, E  pc   c  vg  c
dp

So for photons, group velocity and phase velocity are same.

 QUANTUM MECHANICS
Resolving velocity paradox for matter waves:
Case 1: For a non relativistic free particle, E
p2

dE 2 p mv
  v
2m dp 2m m

So particle velocity and group velocity are same.

Case 2: In relativistic motion, 1
dE 1 
p 2 c 2  m0 c 4 
d 
E p 2 c 2  m0 c 4      p 2 c 2  m0 c 4 
2 2 2 2

dp 2  dp  
1 pc 2 pc 2 p
 vg   2 pc  2
 2
 v
2 p c  m0 c E mc m
2 2 2 4

 vg  v
So in relativistic motion also, the wave packet or wave group travels with the same
velocity as the particle.
Note: We have observed that the superposition of two waves results formation of a
Chain of wave packets. The localization of the particle is not possible with such a chain
of wave packets. But this process of superposition gives an idea that a particle be
represented by a single wave packet which can be constructed by superposing a large
no of waves of slightly differing wavelength and frequency. These waves are so chosen
that, they interfere constructively in a localized region of space and destructively
Elsewhere. If the localization is constant in time, this can represent a particle.
 QUANTUM MECHANICS
Example:
An electron has a De Broglie wavelength of 2 pm. Find its K. E., phase and group
velocities of De Broglie waves.
h hc
Ans: let us first find ‘pc’ of the electron. Since, p   so pc    620keV
Rest energy of the electron is Ee  mec 2  511keV
So K .E.  E  E  E  p c  E   511  620   511 keV  292keV
2 2 2 2 2
e e  e 
If ‘v’ is the velocity of electron, its total energy is given by:
 
 2 
Ee  E  mc  m c E 
E 2 e

2  2 2 
v v v
1 2  1 2 1 2 
c  c c 
 v2  v2 Ee
2
Ee
2
5112
 E 1  2   Ee  2  1  2  v  c 1  2  c 1   0.771c
2 2

 c  c E
2 2
E 803
w E c c
vp      1.30c
Assignment: k p v 0.771c

1. What is phase velocity of a monochromatic wave? Derive an expression for phase

velocity of waves. From this expression, obtain the expression for phase velocity
of De-Broglie waves.
2. Show that phase velocity of de-Broglie waves representing a micro entity, is
different from the velocity of the same entity in its particle representation
(Particle velocity), both in relativistic and non relativistic limit .
 QUANTUM MECHANICS
3. What is velocity paradox?
4 How a group of waves is formed? Considering superposition of two waves of
different wavelength and frequency, obtain the expression for group velocity and
hence obtain the group velocity of de-Broglie waves. Show that group velocity of
de-Broglie waves is equal to the velocity of the entity in particle representation.
5 Obtain the relation between phase velocity and group velocity. Show that for a
non dispersive medium, the phase velocity and group velocity are same.
6. The wavelength of an electron is 25Ǻ. Calculate its kinetic energy. Also obtain its
phase velocity and group velocity.
7. The wavelength of an electron is 10-16 m. Calculate its kinetic energy. Also obtain
its phase velocity and group velocity.
8. Find the phase and group velocity of 8 MeV protons and 8 MeV electrons.
9. For waves in swallow water the phase velocity is about equal to the group
velocity. What is the dependence of phase velocity on wavelength?
10 The wavelength of an electron is 25Ǻ. Calculate its kinetic energy. Also obtain its
phase velocity and group velocity.
11. The wavelength of an electron is 10-16 m. Calculate its kinetic energy. Also
obtain its phase velocity and group velocity.
12. Distinguish between matter waves and electromagnetic waves(or mechanical
waves)
 QUANTUM MECHANICS
We have already discussed how a wave packet is formed. Let us try to give mathematical
Representation to this wave packet.
Consider a wave packet formed by superposition of large no of waves propagating in
x-direction . If we represent the resulting wave function ‘ψ’ at ‘x’ at ‘t’ as ψ(x, t), then:
  x, t    An e i k n x  wn t 
n

Where, An is the amplitude of n-th component wave whose angular frequency is ‘wn ‘
And Wave number is ‘kn ‘ .
If we assume the superposition to be taking place due to waves having a continuum of
Of possible values of ‘k’, then the sum can be replaced by an integration as:

  x, t    Ak e i  kx wt 
dk      (35)

 QUANTUM MECHANICS
The wave packet can be made localized, if the range of ‘k’ values for which the
component waves have significant amplitudes, is limited to a small range ‘k0- Δk’
to ‘k0+Δk’ . Then the wave packet is given by:
k 0  k

  x, t    Ak e i  k x wt dk      (36)

k 0  k
Where we have taken A(k) ≠ 0 for k0- Δk ≤ k ≤ k0+Δk and zero elsewhere.
Note: In the construction of (36), we have assumed that A(k) is narrowly peaked
about some particular value ‘k0 ‘. There is nothing illegal about a broad
spectrum of ‘k’, but it can be seen mathematically that, such wave packets
change shape rapidly, since different components travel at different speeds.
So the whole notion of a group with well defined velocity losses meaning.
Heisenberg's uncertainty principle:
We have seen that a particle in its wave manifestation is represented by a wave packet
Which has a finite spreading. This leads uncertainty in position of particle. To make
position certain, we have to choose small spreading wave packet and for this we need
The component waves must have wave numbers (Δk) that spread over a large range. As
‘p = ħk’, hence, uncertainty in momentum increases.
Heisenberg estimated the limits of accuracy in simultaneous measurement of position
And momentum (position momentum uncertainty principle) or energy and time
(energy-time uncertainty principle)
 QUANTUM MECHANICS
In general, the Heisenberg’s uncertainty principle can be stated as:
“It is impossible to measure simultaneously, with absolute precession, two canonical
Conjugate quantities”.
If ‘p’ and ‘q’ are two canonical conjugate quantities, the product of uncertainty in ‘q’
And ‘p’ is greater than or of the order of ‘ħ/2’.

q  p       (37)
2
(i) Position- momentum uncertainty principle:
It states that, “ It is impossible to measure position and momentum of a particle
Simultaneously with unlimited accuracy”.
If ‘Δx’ is the uncertainty in the position coordinate ‘x’ and ‘Δpx ‘ is the uncertainty in
the x-component of the linear momentum of the particle, then:

x  p x     (38  i )
2
Similarly, applying to ‘y’ and ‘z’ component of position and momentum vectors, we

write y  py     (38  ii)
2

z  p z     (38  iii)
2

(ii) Time-energy uncertainty principle:

It states that,”the product of the uncertainty ‘ΔE’ in the energy measurement and
Uncertainty ‘Δt’ in time at which measurement is made, is equal to or greater than
‘ħ/2’. 
E  t       (39)
2
 QUANTUM MECHANICS
APPLICATIONS OF UNCERTAINTY PRINCIPLE:
1. Non existence of electron in the nucleus:
A typical atomic nucleus is about 5 × 10-15 m in radius. If an electron confines to a
Nucleus, the uncertainty ‘Δx’ in its position is 5 × 10-15 m.
Then as per position-momentum uncertainty principle:
Uncertainty in momentum p    p  1.110 20 kg  m / sec
2x
If this is the uncertainty in the momentum of the electron, the momentum ‘p’ must
be at least comparable in magnitude. An electron with such a momentum has a K.E.
many times greater than its rest energy m0c2. Hence,
12 3.3 1012
K .E.  p c  m0 c  m0c  pc  3.3 10 J  20eV
2 2 2 4 2

1.6 1019
Hence, K.E. of the electron must exceed 20 MeV if it is to be inside the nucleus.
However, experiments show that the electron emitted by certain unstable nuclei
never have more than a small fraction of this energy. Hence electrons cannot reside
inside the nucleus.
2. A source of radio waves emits radio pulses lasting for 0.001 sec. Find uncertainty in
momentum and frequency of photon.
Ans: Each pulse is emitted for 0.001 sec. So length of pulse is:
x  0.001sec c  3 105 m
 QUANTUM MECHANICS
A photon of this radio wave can be any where within this pulse. So uncertainty in
Position of the pulse is 3 × 105 m. Then uncertainty in momentum is:
 1.0541034 J . sec
p    3.511038 kg  m / sec
x 3 10 m
5

h cp
The frequency is related to momentum by: p    
c h
c c h c
   p     103 Hz
h h x x
3. The life time of a given atom in excited state is 10-8 sec. It comes to the ground
state by emitting a photon of wavelength 5800Å. Find the energy uncertainty and
Wavelength uncertainty of the photon.
Ans: The photon can be emitted at any instant during the time interval Δt= 10-8 sec.
Then the energy uncertainty of the photon is:   26
E   1.054  10 J
t
If ‘λ’ is the wavelength of the photon, hc hc  E 
E      hc  2 
 E  E 
So the uncertainty in wavelength is:
 
 
 E   E  2 0
  hc   hc  2 
 E  1.78  10 7
A
 E2 
 hc  
hc
   
  
 QUANTUM MECHANICS
Assignments:
1. State and explain Heisenberg’s uncertainty principle in different forms. Using
uncertainty principle, show that, an electron cannot exist inside a nucleus.
2. An electron of mass 9.1×10-31kg has a speed of 1km/s with an accuracy of 0.05%.
Calculate the uncertainty with which the position of the electron can be located.
3. The uncertainty in the position of a particle is equal to its de-Broglie wavelength.
What is the uncertainty in its velocity?
4. To what accuracy the mass of a meson with life time of 10-23sec can be determined?
5. Calculate the momentum uncertainty of (a) a tennis ball constrained to be in a
fence enclosure of length 35m surrounding the court, and (b) the electron within
the smallest diameter of a hydrogen atom (1.06Å).
6. Calculate the relative (or percentage) uncertainty in velocity and momentum of an
(a) electron and a (b) proton confined to a one dimensional box of length 1.7 nm.
7. What is the bandwidth of an amplifier for radar if it amplifies a pulse of width
2.4 µs?
8. Treating the hydrogen atom as a one dimensional entity of length 0.106 nm,
determine the electron’s minimum kinetic energy.
9. The life time of an excited state can be regarded as an uncertainty in the time δt
associated with a measurement of the energy of the state. This in turn implies an
energy width namely the corresponding energy uncertainty δE. Calculate (a) the
characteristic energy width of such a state, and (b) the uncertainty ratio of the
frequency δf/f , if the wavelength of the emitted photon is 300nm.
 QUANTUM MECHANICS
Waves of what? (Physical significance of matter waves):
The quantity (called as wave function) whose variations make up the matter waves is
purely a mathematical quantity having no physical significance. The value of wave
function ‘ψ’ associated with a moving body at a particular point (x,y,z) at instant ‘t’
Is related to probability of finding the particle at that point at that instant.
“The square of the modulus value of ‘ψ’ *i. e Iψ(x, y, z,t)I2)] is the probability density
at (x, y, z) at instant ‘t’.” *The probability density is defined as the probability of
getting the particle per unit volume). More precisely:
b

 dx gives the probability of finding the particle between ‘a’ to ‘b’ at instant ‘t’.

2

Since the total probability of getting the particle at any instant over the whole region
Of wave packet is one, so: 
  dx  1      (40)
2



A wave function satisfying this condition is called as “normalized wave function”.

Every wave function representing matter waves must be normalized.
 QUANTUM MECHANICS
The Schrodinger equation:
Immediately after the publication of De Broglie hypothesis, Erwin Schrodinger in 1926
Proposed that the behavior of matter waves representing the material particle is
Governed by a certain differential equation for the wave function ‘ψ’ (the function that
represents the matter waves. Schrodinger equation plays the same role in wave
Mechanics as Newton’s second law or Newtonian equation in classical mechanics. We
Cannot rigorously derive Schrodinger equation from existing physical principles,
Rather the equation represents something new standing as first principle in Quantum
Mechanics or Wave Mechanics. The presentation we are going to give here is to show
One route to the wave equation.
Time Dependent Schrodinger equation (One dimensional):
(a) For a free particle:
As discussed earlier, a microscopic entity (like electron, proton, atom…. Etc) can be
represented by a wave packet, which results due to superposition of large no of
Harmonic waves of different wavelength and frequency.
Let us assume the free particle to be represented by a plane wave of the form:
 x, t   Aei kxwt       (41)
Or some linear combination of these type of waves forming the wave packet.
 QUANTUM MECHANICS
The momentum of the free particle and its energy are related with propagation
Number ‘k’ and angular frequency ‘w’ by the relations:
p  k and E  w
Differentiating both sides of eqn. (41) twice with respect to ‘x’:
 2 i ( kx wt )  2  2  2k 2
 k Ae
2
  Ae i ( kx wt )
x 2
2m x 2
2m
 2  2 p2
          (42)
2m x 2 2m
p2
For a free particle(in non relativistic motion): E 
2m
 2  2
  E        (43)
So 2m x 2
Again differentiating equation (41) once with respect to ‘t’ :
 
 iwAe i ( kx wt )  i  wAe i ( kx wt )
t t

 i  E        (44)
t
From (43) and (44), we get:
  2  2
i       (45)
t 2m x 2
This is the time dependent Schrodinger equation for a free particle in one dimension.
 QUANTUM MECHANICS
(ii) For a particle moving under the action of a force field:
If the particle is moving under the action of a force field derivable from a potential
energy ‘V’ given by: F   V
x
p2 p2
Then the total energy of the particle is given by: E  V ( x)   E  V ( x, t )
p 2 2m 2m
Substituting this value of 2m in equation (42),
 2  2 p 2
    E  V ( x, t )
2m x 2 2m
 2  2 ( x, t )
  V ( x, t ) ( x, t )  E ( x, t )    (46)
2m x 2

Then from (44) and (46):

  2  2 ( x, t )
i   V ( x, t ) ( x, t )      (47)
t 2m x 2

Equation (47) is the one dimensional Schrodinger time dependent equation for a
Particle moving in a potential field.
Limitations of Schrödinger equation:
1. It is not applicable to relativistic problems.
2. Mathematical form of P.E. is needed to get the solution.
3. Some times the P.E. function takes the shape, which does not permit to solve the
Schrodinger equation analytically.
 QUANTUM MECHANICS
Time independent Schrodinger equation:
Many times we encounter with the problems, where the potential energy function
does not depend on time, but depends only on space coordinates. In these cases, it
is possible to write the wave function ψ(x,t) as a product of a function ‘u(x)’ of space
coordinates only and a function ‘f(t)’ of time ‘t’ only. i.e
  x, t   u ( x )  f (t )
 2  2u
  f (t )     ( 48  i )
x 2 x 2
 f
&  u ( x)       ( 48  ii)
t t
The time dependent Schrodinger equation is :
  2  2 ( x, t )
i   V ( x, t ) ( x, t )      (47)
t 2m 2x 2
 
Putting the expressions for & from equations (48-i) and (48-ii), we get:
x 2
t
f (t ) 2  2u ( x )
iu ( x)  f (t )  V ( x)u ( x)  f (t )
t 2m x 2
1 f (t )  2 1  2u ( x )
 i   V ( x)
f (t ) t 2m u ( x) x 2
The left hand side of the above equation is a function of ‘t’ and independent of ‘x’,
where as the right side is a function of ‘x’ and independent of ‘t’. This equality is
Possible only when both side is equal to a constant (say ‘E’) independent of ‘x’ and ‘t’.
 QUANTUM MECHANICS
 2 1  2u ( x )
Hence we can write:   V ( x)  E
2m u ( x) x 2
 2  2u ( x )
  V ( x)u ( x)  Eu ( x)
2m x 2
 2  2u ( x)
  E  V ( x) u ( x)  0    ( 48)
2m x 2
This equation (48) is the time independent one dimension Schrodinger equation
Applicable to the problems where the potential energy function ‘V’ depends on
Space coordinates only.
Also we have: 1 f (t )
i E
f (t ) t
f (t )
 i  Ef (t )      (49)
t
f (t ) E iE
  f (t )   f (t )
f (t ) i 
Integrating both sides, we get: iE
 t
f (t )  e 
     (50)
iE

Hence the complete solution is:  x, t   u ( x)  e      (51) 

Remember that this separation is possible only when the potential energy function
‘V’ is a function of space coordinates only.
 QUANTUM MECHANICS
Comments on Schrodinger equation:
1. It is a partial differential equation.
2. It is first order in time derivative and second order in space derivative.
2
  2

(On the other hand, the classical wave equation t  v x is second order in both
2
2
2

space and time derivative)

3. It is a linear differential equation (as it does not contain higher powers of ‘ψ’ and
higher powers of its derivatives.
4. Since the potential energy function is different for different dynamical systems
hence, Schrodinger equation has different solutions for different systems.
5. Since the Schrodinger equation contain imaginary number, hence its solution may
be real or complex. In general they are complex.
(on the other hand solutions of classical wave equation is always real)
Note:
1. Because of the linearity property of Schrodinger equation, its solution obey
following characteristics.
(i) If ‘ψ’ is the solution of Scrodinger equation, a constant times of ‘ψ’ (i.e ‘c ψ’)
also is a solution of Schrodinger equation.
(ii) If ‘ψ1, ψ2, ψ3 …….. Are solutions of Scrodinger equation, then a linear combination
of these i.e c1ψ1+ c2 ψ2+ c3 ψ3 …….(where, c1, c2, c3 …… are constants) is also a
solution of this Schrodinger equation. (This permits the use of superposition
principle to the solutions of Scrodinger eqn. as applicable to classical wave eqn.
 QUANTUM MECHANICS
Physical interpretation of Wave function (Revisited):
The widely accepted physical significance of wave function is the interpretation given
By Max Born which reads as:
1. The wave function ‘ψ’ in general is a complex quantity having no physical
significance. But the product of ‘ψ(x,t)’ with its complex conjugate ‘ψ*(x,t)’ gives
the probability density of finding the particle at a point ‘x’ at instant ‘t’
So  ( x, t ) gives the probability density at ‘x’ at ‘t’. So  ( x, t ) dx gives the
2 2

probability of finding the particle in a small length ‘dx’ at instant ‘t’.

2. As the particle is definitely present some where in the whole space, hence the
total probability integrated over the whole space must be one.i.e


  dx  1      (40)
2



A wave function that satisfies condition (40) is called as normalized wave function.
Note: If the solution of Schrodinger equation is not normalized, then it can be
normalized as follows:
 
Let,   dx  N   N
2 1
 ( x, t ) ( x, t ) dx  1
*

 

 1  1 
   * ( x, t )   ( x, t )   1
  N  N 

 1 
 ( x, t )    ( x , t )
Writing  , We have  ( x, t ) ( x, t )dx  1 , where, φ(x,t) is normalized
*
 N 

solution of Schrodinger equation.
 QUANTUM MECHANICS
Note: The wave function ‘ψ’ (i.e the solution of Scrodinger equation) for which the
integral   dx exists and gives a finite value is called as square integrable.
2

General Features of Acceptable Solutions in one dimensional problem:

1. The wave function ‘ψ’ must be finite, continuous and single valued at all points of
space.
2. The first derivative of ‘ψ’ is finite, continuous and single valued at all points where
V(x) is finite.
3. ‘ψ‘ must be square integrable so that ‘ψ* ψ‘ is finite.
4.   0 At the points where V ( x, t )  0
Difference between matter wave and electromagnetic waves:
1. In electromagnetic waves, electric field and magnetic field oscillates, whereas, in
matter waves, a quantity with no physical significance oscillates.
2. Electro magnetic waves are governed by classical wave equation (or Maxwell eqns.)
Whereas, matter waves are governed by Schrodinger equation.
Stationary State:
When the potential energy in a problem is independent of time, then, the wave function
is given by: 
iE

iE

iE
 ( x, t )  u( x)e     *  u( x)e  u* ( x)e  u ( x)
 2  2

Then the probability density at any point is independent of time. A state of the system
In which the “probability density” is independent of time is called as “stationary state”.
 QUANTUM MECHANICS
Then the solutions of Schrodinger equations are called as stationary state
solutions.
In stationary states, the energy of the system remains independent of time.
The appropriate Schrodinger equations for such a system is Time-Independent
Schrodinger equation.
ASSIGNMENT:
1. Give the significance of wave function for matter waves?/ Give an account of the
probabilistic interpretation of the wave function.
2. Outline the characteristics of the wave function. (What are the requirements of
acceptable (well behaved) wave function?).
3. What do you mean by normalization of a wave function? Why the acceptable
wave function should be normalized?
4. Establish time dependent Schrödinger’s equation in one dimension. How the
effect of external conservative force is incorporated into the equation?
5. Establish time-independent Schrodinger’s equation in one dimension.
6. What do you mean by stationary state? Is the wave function representing a
stationary state independent of time? Explain.
7. Show that the probability density for a stationary state is independent of time.
 QUANTUM MECHANICS
Applications of Schrödinger equation:
Many real problems encountered in atomic, molecular, nuclear and solid state physics
Are three dimensional but can be reduced to equivalent one dimensional problems.
Various aspects of the bound states and free states of a micro system can be
understood easily from the study of these reduced one dimensional problems. Hence,
we shall here Restrict ourselves to the application of Schrodinger equation to one
dimensional Problems only. We shall only discuss those problems, where the potential
energy function is independent of time (but depends on space coordinates only). Then
the appropriate Schrodinger equation is time independent one and solutions are
Steady state solutions.
Note: An important property of the Schrodinger’s time independent equation that, if it
has one or more solutions for a given system, each of these wave functions
Corresponds to a specific value of energy. Thus energy quantization appears in wave
mechanics as a natural consequence of the theory. The values of energy En for which
Schrodinger steady state equation can be solved as Eigen values and the corresponding
wave functions ‘ψn ‘ are called as Eigen functions.