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Contents

1. Failures of the classical theory

a. Maxwell’s equations and electromagnetic waves
b. Blackbody radiation
c. Atomic spectra
2. Dual nature of radiation – Compton Effect
3. Matter waves
4. Double slit experiment with particles
5. Heisenberg’s uncertainty principle
6. Concepts of wave functions

1. Maxwell’s equations in a Dielectric medium

Maxwell summarized the existing ideas of electric and magnetic fields and their inter-related
phenomena into four equations (in 1860) which are known as the Maxwell’s equation. This also
paved the way for describing radiation as an electromagnetic wave.

Integral form Differential form

Gauss’s law for electric charges

1. Gauss’s law states that the integral over the 1. Divergence of the electric field is given by
closed surface of the electric field normal to the charge density divided by 𝜺𝒐
the surface should be a measure of the 𝝆
𝛁. 𝑬 = ( Gauss’ law for electric fields)
charge enclosed by the 𝜺𝒐
surface

Gauss’s law for magnetic charges

2. Since magnetic mono poles do not exist and 2. Divergence of the magnetic field is uniformly
the magnetic lines of force are continuous zero
the integral form of Gauss’s 𝛁. 𝑩 = 𝟎 ( Gauss’ law for magnetic fields)
law for magnetic fields

Faraday’s law of electromagnetic induction

3. A time varying magnetic field induces an 3. The curl of the electric field is equal to the
electric field in a closed loop enclosing a rate of change of the magnetic field which is
surface described by the standard Faraday’s law of
𝝏𝑩
electromagnetic induction. 𝛁𝐱𝑬 = −
𝝏𝒕

Ampere - Maxwell circuital law (Ampere’s law modified by Maxwell )

4. An electric current or a changing electric flux 4. The curl of the magnetic field is given by the
through a surface produces a circulating current density through the closed loop and
magnetic field around any path that bounds the displacement current
that surface 𝝏𝑬
𝛁𝐱𝑩 = 𝝁𝒐 𝒋 + 𝝁𝒐 𝜺𝒐 𝝏𝒕
This equation is an extension of the
Ampere’s law with the addition of the
displacement current when there was a
component of time varying electric fields

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…………………………………………………………………………………………………………………..
[A review of the operations with the 𝛻 operator (nabla operator)
𝜕 𝜕 𝜕
The 𝛻 operator is a partial differential mathematical operator and is given by 𝛻 = 𝑖 𝜕𝑥 + 𝑗 𝜕𝑦 + 𝑘 𝜕𝑧
where 𝑖 , 𝑗, 𝑎𝑛𝑑 𝑘 are the unit vectors in the three orthogonal directions.
𝜕 𝜕 𝜕
The operator 𝛻 = 𝑖 + 𝑗 +𝑘 when operates on a scalar quantity gives rise to a vector. For
𝜕𝑥 𝜕𝑦 𝜕𝑧
example the 𝛻 operator operating on an electric potential gives the electric field at the point

𝝏𝑽𝒙 𝝏𝑽𝒚 𝝏𝑽𝒛

𝛻𝑽 = 𝒊 + 𝒋 +𝒌 = 𝒊 𝑬 𝒙 + 𝒋𝑬𝒚 + 𝒌𝑬𝒛 = 𝑬
𝝏𝒙 𝝏𝒚 𝝏𝒛

The dot product of the 𝛻 operator with another vector field gives rise to the divergence of the defined
field or the rate of change of the field in the three orthogonal directions.

The cross product of 𝛻 operator with a vector field gives the curl of the field and results in a vector
which is perpendicular to both 𝛻 and the given vector.

Another important identity with the 𝛻 operator is the curl of the curl of a vector ie.,

𝜵𝐱𝜵𝐱𝑬 = 𝜵 𝜵. 𝑬 − 𝜵𝟐 𝑬
𝜕2 𝜕2 𝜕2
where 𝛻 2 = 𝜕𝑥 2
+ 𝜕𝑦 2 + 𝜕𝑧 2 is the scalar Laplacian operator.]

Maxwell’s equations in free space

In the case of free space (which does not have sources of charges and currents) then the
Maxwell’s equations reduce to

𝛁. 𝑬 = 𝟎 …..……………………………………… (1)
𝛁. 𝑩 = 𝟎 …………………………………………. (2)
𝝏𝑩
𝛁𝐱𝑬 = − …………………………………………. (3)
𝝏𝒕
𝝏𝑬
𝛁𝐱𝑩 = +𝝁𝒐 𝜺𝒐 …………………………………………. (4)
𝝏𝒕
Taking the curl of curl of the electric field the equation can be written as

𝝏𝑩
𝛁× 𝛁×𝑬 = 𝛁× − this reduces to
𝝏𝒕

𝝏𝛁×𝑩
𝛁(𝛁. 𝐄) − 𝛁 𝟐 𝐄 = − 𝝏𝒕

𝝏𝛁×𝑩
Since 𝛁. 𝑬 = 𝟎 this reduces to −𝛁 𝟐 𝐄 = −
𝝏𝒕

𝝏𝟐 𝐄𝟐
Substituting for curl of B the above equation simplifies to 𝛁 𝟐 𝐄 = 𝝁𝒐 𝜺𝒐 .
𝝏𝒕𝟐

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𝟏
But we know that 𝝁𝒐 𝜺𝒐 = 𝒄𝟐 and the equation reduces to

𝟏 𝝏𝟐 𝑬
𝛁𝟐𝐄 = which is the general form of a wave equation. Maxwell concluded that this
𝒄𝟐 𝝏𝒕𝟐
1
should be an electric vector in free space travelling at the speed of light 𝑐 = 𝝁𝒐 𝜺𝒐

In a very similar way we could starting from the curl of the curl of the magnetic field show that

𝟏 𝝏𝟐 𝑩
𝛁𝟐𝐁 = . This describes a transverse magnetic field vector travelling at the speed of
𝒄𝟐 𝝏𝒕𝟐
light.

The electric and magnetic waves must therefore be representing light and hence Maxwell
proposed that light could be treated as electromagnetic waves, where the electric and magnetic
vectors are mutually perpendicular and perpendicular to the direction of propagation of the
radiation.

Consider a 1D electric wave Ex associated with radiation propagating in the Z direction which can
be represented as

𝑬𝒙 = 𝑨 𝐜𝐨𝐬(𝝎𝒕 + 𝒌𝒛)

This implies that the electric field vector has only an x component and the other two components
Ey and Ez are zero.

Hence the associated magnetic component of the EM wave can be evaluated using the Maxwell’s
𝝏𝑩
third equation namely 𝛁𝐱𝑬 = −
𝝏𝒕

𝒊 𝒋 𝒌
𝝏 𝝏 𝝏 𝝏𝑬𝒙
Evaluating the curl of the electric field 𝛁𝐱𝑬 = =𝒊×𝟎+𝒋∗ 𝝏𝒛
+𝒌∗𝟎 =
𝝏𝒙 𝝏𝒚 𝝏𝒛
𝑬𝒙 𝟎 𝟎
𝝏
𝒋 𝝏𝒛
𝑨 𝐜𝐨𝐬 𝝎𝒕 + 𝒌𝒛 = 𝒋 ∗ 𝒌 ∗ 𝑨𝒔𝒊𝒏(𝝎𝒕 + 𝒌𝒛)

𝝏𝑩
this implies that − 𝝏𝒕
= 𝒋 ∗ 𝒌 ∗ 𝑨𝒔𝒊𝒏(𝝎𝒕 + 𝒌𝒛)

Integrating the above equation with respect to time t we get

𝟏 𝟏 𝟏
𝑩 = 𝒋 ∗ 𝒌 ∗ 𝑨𝒄𝒐𝒔 𝝎𝒕 + 𝒌𝒛 ∗ = 𝒋 ∗ 𝑨𝒄𝒐𝒔 𝝎𝒕 + 𝒌𝒛 ∗ 𝝎 = 𝒋. 𝑬 𝒙 ∗ 𝒄
𝝎
𝒌

since 𝑐 = 𝜔/𝑘 is the velocity of the radiations. We note that the magnetic component of the EM
𝟏
wave has only the Y component and the magnitude of the wave is times the magnitude of the
𝒄
electric component of the wave. Thus we conclude that the EM waves have a coupled electric and
magnetic field components which are mutually perpendicular to each other and both are
perpendicular to the direction of propagation of radiation.

Energy of EM waves

Classically the energy of waves is equivalent to it’s intensity which is square of the amplitude of
the waves.
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The energy associated with an Electric field per unit volume of free space is 𝐸𝑛 = 𝜺 𝑬𝟐
2 𝒐
where E
is the electric field.
1 1
The energy content of the electric component of the wave = 𝜺 𝑬 𝟐
2 𝒐 𝒙
= 2 𝜺𝒐 𝑬𝒐𝒙 𝟐 𝐜𝐨𝐬 𝟐(𝝎𝒕 + 𝒌𝒛)
𝟐
𝟏 𝑩𝒚 𝟏 𝑬 𝟐 𝟏
The energy content of the magnetic component of the wave =
𝟐 𝝁𝒐
= 𝟐 𝒄𝟐𝒙𝝁 = 𝜺 𝑬 𝟐
𝟐 𝒐 𝒙
𝒐

Hence the total energy content of the wave is the sum of the two components = 𝜺𝒐 𝑬𝒙 𝟐 .

Poynting Vector

EM waves carry energy in the direction perpendicular to the E and B field variations and is
𝟏
described by the Poynting vector 𝒔 ≡ 𝒄𝟐 𝜺𝒐 𝑬 × 𝑩 = 𝝁 𝑬 × 𝑩
𝒐

Ex is however a time varying component and hence to determine the average energy of the wave
transmitted per unit time through unit area can be found out as
T T
cεo 2 cεo
Average Energy < 𝑆 > = Ex dt = 𝑬𝒐𝒙 𝟐 𝐜𝐨𝐬𝟐 𝝎𝒕 + 𝒌𝒛 dt
T 0 T 0

1 2 1 Boy 2 1 Eox Boy

= εo cEox = c =
2 2 μo 2 μo
This implies that the average energy content of EM waves to be proportional to the square of the
amplitude of the electric or magnetic vector and is independent of the frequency of the waves.
Thus the classical picture of the EM waves as carriers of energy gives a picture of frequency
independence. For this reason some of the observed phenomena of interaction of light with matter
could not be consistently explained in spite of the fact that all other observed phenomena of
radiation could be explained by the Maxwell’s EM wave theory.

Polarisation states of EM waves

Light is a transverse electromagnetic wave, but natural light is

generally unpolarized, all planes of propagation being equally
probable.

Light in the form of a plane wave in space is said to be linearly polarized. The
addition of a horizontally linearly polarized wave and a vertically polarized wave of the
same amplitude in the same phase result in a linearly polarized at a 45o angle

If light is composed of two plane waves of equal amplitude but differing in phase by
90°, then the light is said to be circularly polarized.

If two plane waves of differing amplitude are related in phase by 90°, or if the relative
phase is other than 90° then the light is said to be elliptically polarized.

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2. Black body radiation in equilibrium

Classically the interaction of radiation with matter with radiation is manifested in the way materials
absorb radiations, emitted characteristic wavelengths which gives the color of the material.

Gustav Robert Kirchhoff studied the absorption properties of materials and found
materials which absorb all incident rays. If such a material is heated then it would
emit all wavelengths of radiation as it absorbed. Such a material is defined as a
black body.

A black body is also modeled as a cavity which does not allow any incident radiation to escape due to
multiple reflections inside the cavity. This cavity when heated radiates emit radiation of every
possible frequency at a rate which increases with temperature of the body. The amount of radiant
energy does not increase monotonically with time but is limited
by the rate at which the radiation is also absorbed by the cavity.
The amount of energy emitted at a frequency is limited by the
thermodynamic equilibrium of the absorption and emission
processes. It was also observed that the radiation density in an
equilibrium state depends only on the temperature of the walls
of the cavity and does not depend on the material or structure of
the wall. The distribution as well as the characteristic maximum
wavelength shifts to the lower wavelength side.

The emission from the blackbody at different temperatures can

be modeled as due to emissions from harmonic oscillators on the
surface of the walls of the cavity. Due to physical dimension of the
cavity being large and the number of harmonic oscillators on the
surface of the cavity is also large, a large range of wavelengths can
be emitted. The emission from the cavity is limited to those
radiations which can form standing waves in the cavity. Consider a
cubical cavity of side a. The wavelengths of the oscillations that can resonate in the cavity has to
𝝀
satisfy the condition 𝒂 = 𝒏 .
𝟐

c c
Or the frequencies that can sustain in the cavity is given by ν = λ
=n 2a

𝒄
The additional no. of frequencies 𝒅𝝂 when n changes to dn is 𝒅𝝂 = 𝒅𝒏
𝟐𝒂

In a three dimensional cavity the number of frequency states that can resonate in the cavity is
𝒄
estimated as 𝝂 = 𝒓 𝟐𝒂
where 𝒓 = 𝒏𝟐𝒙 + 𝒏𝟐𝒚 + 𝒏𝟐𝒛 is the radius of a surface in n space for allowed
values of nx , ny and nz. This surface is an octant of a sphere of radius r. The volume of this octant is a
measure of the number of frequency states in the cavity up to the allowed nx , ny and nz
𝒄
The additional no. of frequencies 𝒅𝝂 when r changes to dr is 𝒅𝝂 = 𝒅𝒓 𝟐𝒂

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The energy density of radiations can be estimated if the number oscillators and their average energy
can be estimated. In the case of a cavity of volume V we can estimate the number of oscillators with
𝟖𝝅𝑽 𝟐
frequencies between 𝝂 𝒂𝒏𝒅 𝝂 + 𝜹𝝂 as 𝒅𝑵 = 𝒄𝟑
𝝂 𝒅𝝂.

Thus the density of frequency states (number of states per unit volume) with frequencies between
𝟖𝝅 𝟐
𝝂 𝒂𝒏𝒅 𝝂 + 𝜹𝝂 as 𝒅𝑵 = 𝝂 𝒅𝝂
𝒄𝟑

The Boltzmann distribution function describing the probability of a large number of oscillators with
−𝑬
𝒆 𝒌𝑻
energy E in thermal equilibrium at temperature T is given by 𝑷 𝑬 = .
𝒌𝑻

Rayleigh and Jeans estimated the average energy of the oscillators using the Boltzmann distribution
𝑬∗𝑷 𝑬 𝒅𝑬
function as 𝑬 =
𝑷 𝑬 𝒅𝑬

This integral for E varying from 0 to infinity gives the equi-partition of energy 𝑬 = 𝒌𝑩 𝑻.

Thus the energy density (energy per unit volume) of radiations with frequencies between 𝝂 𝒂𝒏𝒅 𝝂 +
𝜹𝝂 can be estimated as
𝟖𝝅 𝟐
𝝆 𝝂 𝒅𝝂 = 𝑬 ∗ 𝒅𝑵 = 𝒄𝟑
𝝂 𝒅𝝂𝑘𝐵 𝑇 .

This predicts that the intensity of radiations of a particular frequency should increase as 𝝂𝟐 and at
very high frequencies the intensities must be infinite at any temperature T. This is the Rayleigh
Jeans law which is in contradiction with the experimental observations and termed as the ultra violet
catastrophe.

A solution to this problem was provided by Max Planck in 1900 when he proposed that the energy of
the harmonic oscillator are restricted to multiples of the fundamental natural frequency 𝝂 times a
constant (𝑕 = 6.6𝑥10−34 𝐽𝑠) ie., 𝑬 = 𝒏𝒉𝝂. Thus the radiations are from a collection of harmonic
oscillators of different frequencies and the energy of the radiations from the oscillators has to be
packets of 𝒉𝝂. Hence the average energy has to determined as a summation of the probabilities of
−𝒏𝒉𝝂
𝒆 𝒌𝑻
𝑬∗𝑷 𝑬 𝒅𝑬 𝒏𝒉𝝂 𝒅𝑬
the energy of the individual oscillators to the total probability as 𝑬 = = −𝒏𝒉𝝂
𝒌𝑻
𝑷 𝑬 𝒅𝑬 𝒆 𝒌𝑻
𝒅𝑬
𝒌𝑻

With this concept of energy of the radiations the average energy of the oscillators can be evaluated
−𝒉𝒗
𝒉𝝂∗𝒆 𝒌𝑻
as 𝑬 = −𝒉𝒗 and the energy density of radiations can be evaluated as
𝟏− 𝒆 𝒌𝑻

𝟖𝝅 𝟐 𝒉𝝂 𝟖𝝅𝒉𝝂𝟑 𝟏
𝝆 𝝂 𝒅𝝂 = 𝑬 𝒅𝑵 = 𝟑
𝝂 𝒅𝝂 𝒉𝒗
= 𝟑 𝒉𝒗
𝒅𝝂
𝒄 𝒆 𝒌𝑻 − 𝟏 𝒄 𝒆 𝒌𝑻 − 𝟏
The decrease in the intensity at higher frequencies (smaller wavelengths) can be attributed to the fact
that the excitation of the oscillators to the higher energy states is less probable at lower temperatures.
At higher temperatures the thermal energy 𝑘𝑇 enables oscillations at higher frequency 𝑛𝝂. This
expression gives excellent co-relation with experimental results which was a milestone. At very low
frequencies this expression reduces to the Rayleigh Jeans expression.

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Thus Max Planck had unknowingly laid the foundation for quantization of energy states of a system
though not in the currently understood terminologies.

Atomic Spectra

Atoms of different elements have distinct spectra and therefore atomic spectroscopy allows for the
identification and quantization of a sample's elemental composition.

Robert Bunsen and Gustav Kirchhoff discovered new elements by observing their emission spectra.
Atomic absorption lines are observed in the solar spectrum and referred to as Fraunhofer lines after
their discoverer. The existence of discrete line emission spectra or the absence of discrete lines in an
absorption spectra puzzled scientists since the atomic model had not evolved at the time of these
observations.

Classical physics tried to model the emission from atoms as that due to the orbiting electron, since an
accelerated charge should emit electromagnetic radiation --- light. However according to this model
the electron should be continually losing energy and fall into the atom in an extremely small time
interval.

(The explanation of the line spectrum of atoms in terms of transition between energy states of an
atom evolved after the quantum model of the atom
evolved.) Photo electric effect – an experiment in which radiation
(electromagnetic waves) interact with matter where
Dual nature of radiation emission of electron from the metal when radiation of
wavelengths lesser than a cutoff wavelength. The
Radiation is part of the electromagnetic spectrum electron emission was instantaneous and the kinetic
energy of the emitted electrons depended only on the
and can be described as electromagnetic waves. wavelength of the incident radiation and not on the
intensity.
Electromagnetic waves are construed as mutually
perpendicular sinusoidal electric and magnetic These results could not be explained on the basis of the
classical EM wave theory. The classical theory
fields and perpendicular to the direction of suggests that electrons accumulate of energy from the
propagation of the waves. The classical concept incident waves on continuous irradiation and when the
energy of the electrons is more than the work function
assumed that the energy content of the wave is of the material it is emitted from the metal after a
proportional to the square of the amplitude of the delayed time. According to the classical theory the
kinetic energy of the electrons emitted should be
waves. The wavelength (and hence the frequency) dependent on the intensity of the radiation and
independent of the wavelength. All these explanations
are not of any consequence with regard to the were in contradiction to the experimental results.
energy of the wave. Conventional wave theory of
Einstein explained the effect considering light to
radiation explains the phenomena of reflection, behave as particles called Photons and the interaction
refraction, interference, diffraction and polarization of the photons with the electrons in the metal can result
of light. Interference and diffraction though stands in transfer of energy to the electron. If the energy
gained by the electron is greater than the work function
out as an exclusive wave property. of the metal, then the electron can be emitted and the
kinetic energy of the photo electron would depend on
The Photo electric effect was explained by Einstein the energy of the incident photon. This was a classic
as a particle - particle interaction. This paved the example of radiation displaying a particle nature when
the interaction is at atomic / sub atomic particles.
wave for the concept of the dual nature of
radiations. The particle nature of radiations could
be evident when radiation interacted with matter at the atomic / sub atomic level.

Compton effect :

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Arthur H Compton while studying the scattering of X rays by Relativistic concepts of energy and
materials observed that in addition to the emission of an momentum of particles
electron, the scattered beam has a different wavelength as Einstein’s concepts of relativistic
compared to the incident wavelength. particles (particles moving with
speeds comparable to the speed of
The scattering of X rays (the high energy end of the light) are
electromagnetic spectrum) if treated classically would not  A particle it at rest it has a rest
2
explain the origin of X rays of higher wavelength. mass energy given by E= moc .
 A particle moving with a velocity
Compton treated the problem as a particle -particle collision v will have a mass given by
𝒎𝒐
𝑕 𝒎=
in which photons of momentum 𝑝𝑖 = 𝜆 are scattered with an 𝟏−
𝟐 𝒗
𝑖 𝒄𝟐
electron at rest. This results in a transfer of momentum and  If p is the momentum of the
energy to the electron which is scattered. The photon loses particle then the kinetic energy
of the particle is given by pc
energy and momentum which results in an gain in
 The total energy of the particle
momentum and energy for the electrons. The scattered X-
is given by 𝑬 = 𝒑𝟐 𝒄𝟐 + 𝒎𝒐 𝟐 𝒄𝟒
ray photon has reduced energy which results in an increase
in the wavelength.

The analysis of the conservation of energy and momentum conservation before and after the collision
(taking into consideration the relativistic effects for the energy and momentum of the electron) gives
the increase in the wavelength of the scattered photon.
𝑕
If 𝜆𝑖 is the wavelength of the incident X-ray photon, the momentum of the photon is 𝑝𝑖 = and the
𝜆𝑖
𝒉𝒄
energy of the photon is 𝑬𝒊 = 𝝀𝒊
. Since the electron is at rest
the initial momentum of the electron is zero and the energy of
the electron is the rest mass energy moc2.
After the collision the wavelength of the scattered X ray is 𝜆𝑓
𝑕
and the momentum 𝑝𝑓 = 𝜆 . The energy of the scattered X
𝑓
𝒉𝒄
ray is 𝑬𝒇 = .
𝝀𝒇

The momentum of the scattered electron is 𝑝𝑒 and the

energy is 𝑬𝒆 = 𝒑𝒆 𝟐 𝒄𝟐 + 𝒎𝒐 𝟐 𝒄𝟒
The energy conservation equation is 𝒑𝒊 𝒄 + 𝒎𝒐 𝒄𝟐 = 𝒑𝒇 𝒄 + 𝒑𝒆 𝟐 𝒄𝟐 + 𝒎𝒐 𝟐 𝒄𝟒
From this expression we get 𝒑𝒆 𝟐 = 𝒑𝒊 𝟐 + 𝒑𝒇 𝟐 − 𝟐𝒑𝒊 𝒑𝒇 + 𝟐𝒎𝒐 𝒄 𝒑𝒊 − 𝒑𝒇 …(i)
Since the X ray and the electron are scattered in different directions, the momentum conservation
equation has to be treated as conservation of the momentum of the particles before and after
collisions in the direction of incidence and in a perpendicular direction.
Momentum conservation along the incident direction is 𝒑𝒊 + 𝟎 = 𝒑𝒇 𝒄𝒐𝒔𝜽 + 𝒑𝒆 𝒄𝒐𝒔𝝓.
Hence 𝒑𝒆 𝒄𝒐𝒔𝝓 = 𝒑𝒊 − 𝒑𝒇 𝒄𝒐𝒔𝜽 ..(ii)
Momentum conservation in a perpendicular direction is 𝟎 = 𝒑𝒇 𝒔𝒊𝒏𝜽 − 𝒑𝒆 𝒔𝒊𝒏𝝓
Or 𝒑𝒆 𝒔𝒊𝒏𝝓 = 𝒑𝒇 𝒔𝒊𝒏𝜽 …(iii)
Squaring and adding equation (ii) and (iii) we
𝒑𝒆 𝟐 = 𝒑𝒊 𝟐 + 𝒑𝒇 𝟐 − 𝟐𝒑𝒊 𝒑𝒇 𝒄𝒐𝒔𝜽 …(iv)

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Comparing equations (i) and (iv) we obtain −𝟐𝒑𝒊 𝒑𝒇 + 𝟐𝒎𝒐 𝒄 𝒑𝒊 − 𝒑𝒇 = −𝟐𝒑𝒊 𝒑𝒇 𝒄𝒐𝒔𝜽 which can be
𝒉
simplified to 𝝀𝒇 − 𝝀𝒊 = 𝚫𝝀 = 𝒎 𝟏 − 𝐜𝐨𝐬 𝜽
𝒆𝒄

The change is the wavelength 𝚫𝛌 = 𝝀𝒇 − 𝝀𝒊 is known as the

Compton Shift.

It is obvious that the Compton shift Δ𝜆 is

 independent of the incident wavelength of X rays

 independent of the type of the scattering material
 depends only on the angle of scattering of the X rays
𝑕
The term is termed as the Compton wave length 𝛌𝐜 and is a
𝑚𝑒𝑐
constant =2.42 x 10-12 m.

At θ=0o we notice there is no shift in the wavelength or there is no

interaction of the X rays with the electrons.

At θ=90o the shift 𝚫𝛌 = 𝛌𝐜

At θ=180o the collision is a head on collision and the shift in the wavelength is maximum 𝚫𝛌 = 𝟐𝛌𝐜.
Thus we conclude that maximum momentum and hence energy transfer happens when the incident
X ray is back scattered.

At other angles the predicted shift were in agreement with the experimental observations.

Thus the Compton Effect was another instance of the particle nature of radiation.

The two experiments of interaction of radiation with matter at sub atomic levels (Photo electric effect
and the Compton effect) led to the conclusion that radiation exhibit a dual nature - show the normal
wave characteristics and a particle at times of interaction of radiation with matter.

Young’s double slit experiment with particles

A double slit experiment with a particles incident on the slits

one at a time reveal some interesting outcomes. Experiments
show that electrons (or photons) as particles are expected to
arrive at some definite location on a screen, unlike a wave.
But if a second electron (or photons) is incident at the slit, the
second electron reaches a different location, often far outside
any experimental uncertainty. If many electrons (or photons)
are incident on the slit but one at a time then the
measurements will display a statistical distribution of
locations that appears like an interference pattern.

The building up of the diffraction pattern of electrons

scattered from a crystal surface. Each electron arrives
at a definite location, which cannot be precisely
predicted. The overall distribution shown at the bottom
can be predicted as the diffraction of waves having the
de Broglie wavelength of the electrons.

This experiment leads to concept of probabilities that

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are inherent in quantum mechanical systems. A quantum particle exhibits probabilistic behavior when
there is no effort to detect the particle.

Dual nature of matter

Louis de Broglie (analyzing the results of the dual nature of radiation) put forward the hypothesis that
matter (form of energy) when in motion can display wave characteristics and the wavelength
𝒉
associated with the moving particle 𝝀 = 𝒎𝒗 where mv is the momentum of the particle.

Common heavier particles have a wavelength that is beyond the measurement capabilities with the
best of techniques available. For example the wavelength of a carbon atom moving with a velocity of
100m per second could possess a wavelength of the order of 10-10m. This has to be measured with
an experiment characteristic of waves such as diffraction or interference.

The wavelength of the associated waves has to be in the measureable range of an interference or
diffraction experiment to prove the existence of matter waves.

This concept was experimentally verified by Davisson and Germer who observed unusual scattering
characteristics for electrons scattered by a Ni crystal when the accelerating potential of the electrons
was 54V and angle of scattering 50o.

The de Broglie wavelength of electrons accelerated by 54V can be estimated to be 1.67 x 10-10m. If
the electron wave possess such a wavelength, it should be possible to diffract the waves with a
known crystal.

If the scattering has to be explained as a diffraction phenomena (characteristics of waves) following

Bragg’s law, then 𝟐𝒅 𝐬𝐢𝐧 𝜽 = 𝒏𝝀 where d in the interplanar distance of the Ni crystal, 𝜃 the glancing
angle (angle between the incident ray and the surface of the crystal) and 𝜆 is the wavelength of the
“waves”.

This yields a wavelength which is close to the value obtained using de Broglie’s hypothesis (matter
waves). Since diffraction is characteristic of waves, it was concluded that electrons undergo
diffraction under the set experimental conditions.

Thus it is concluded that matter display dual characteristics at appropriate conditions of interaction.
This concept has been further confirmed by diffraction experiments using heavier particles such as
the slow neutrons from a nuclear reactor.

Hitachi in the 1980s showed the diffraction of electrons when scattered by a thin wire. It was
observed that the electrons scattering patterns are very close to a diffraction pattern produced by a
double slit experiment.

Wave packets

The concept of matter waves requires a wave like (mathematical)

representation of the moving particle where position and momentum of
the particle can be estimated with reasonable accuracy. Sinusoidal
representations result in a gross uncertainty in the position while
providing a highly accurate estimation of the momentum.

The superposition of two waves of very close frequency and propagation

constant results in a wave packet, frequency 𝜔 + 𝛥𝜔 and propagation
constant 𝑘 + 𝛥𝑘. Let y1 be a sinusoidal wave with angular frequency ω
and propagation constant k and y2 be a wave with frequency 𝜔 + 𝛥𝜔 and

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propagation constant k+Δk.

𝑦1 = 𝐴sin⁡
(𝜔𝑡 + 𝑘𝑥) and

𝑦2 = 𝐴 sin{ 𝜔 + Δ𝜔 𝑡 + 𝑘 + Δ𝑘 𝑥}

The superposition of the two waves gives a resultant

Δ𝑤𝑡 +Δ𝑘𝑥
𝑦 = 𝑦1 + 𝑦2 = 2𝐴𝑠𝑖𝑛 𝑤𝑡 + 𝑘𝑥 . cos⁡
( 2
)

The first part is the original high frequency component and the second term is a low frequency
component. This is the case of an amplitude modulated wave where the amplitude of the high
frequency component is modulated according to the amplitude of the low frequency component.
Since this is the resultant of a group of super imposed waves, it is referred to as a wave packet.

The momentum of the particle could be evaluated with the estimation of the wavelength of the waves
in the wave packet. The position of the particle could be inferred from the region in which the
amplitude (and hence the intensity) of the wave is a maximum.

This gives a reasonably accurate value of both momentum and position. The momentum is derived
from the wavelength of the high frequency component and the position from the region of maximum
amplitude of the wave packet.

We can define both a phase and group velocity for the wave packet.

The phase velocity of the waves is defined as the velocity of an arbitrary point marked on the wave
𝝎
and is given be 𝒗𝒑 =
𝒌

𝒅𝝎
Group velocity is defined as the velocity of the wave packet (wave group) and is given by 𝒗𝒈 = .
𝒅𝒌

Relation between group velocity and particle velocity

𝑑𝜔
Group velocity of waves = 𝑣𝑔 = 𝑑𝑘
𝐸 𝑑𝐸
The angular frequency 𝜔 = ℏ
where E is the energy of the wave and hence 𝑑𝜔 = ℏ
𝑝 𝑑𝑝
The wave vector 𝑘 = ℏ where p is the momentum and hence 𝑑𝑘 = ℏ
𝑑𝜔 𝑑𝐸
Therefore the group velocity 𝑣𝑔 = 𝑑𝑘
= 𝑑𝑝
𝑝2 𝑑𝐸 𝑝
Since 𝐸 = 2𝑚 the group velocity 𝑣𝑔 = 𝑑𝑝
= 𝑚 = 𝑣 where v is the particle velocity.

Relation between group velocity and phase velocity

𝑑𝜔 𝑑 𝑑𝑣𝑝 𝑕
The group velocity of the particle is given by 𝑣𝑔 = 𝑑𝑘
= 𝑑𝑘
𝑣𝑝𝑕 . 𝑘 = 𝑣𝑝𝑕 + 𝑘 𝑑𝑘

𝒅𝒗𝒑𝒉 𝒅𝒗𝒑𝒉 𝒅𝝀
However
𝒅𝒌
= . .
𝒅𝝀 𝒅𝒌

𝑑𝜆 2𝜋 𝟐𝝅 𝒅𝒗𝒑𝒉 𝒅𝒗
And
𝑑𝑘
= − 𝑘 2 hence 𝒗𝒈 = 𝒗𝒑𝒉 − 𝒌 𝒅𝝀
= 𝒗𝒑𝒉 − 𝝀 𝒅𝝀𝒑𝒉

In a dispersive medium (where the velocity of the waves depends on the wavelength) the group
velocity is given by the above equation.

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When the group velocity of the wave packet is equal to the phase velocity the medium in which the
𝒅𝒗𝒑𝒉
wave propagate is a non dispersive medium. In this case 𝒅𝝀
= 𝟎 or the phase velocity is a constant
with respect to wavelength.

Evaluate the condition under which the group velocity of a wave packet is

i) Half the phase velocity and ii) twice the phase velocity
𝑑𝑣𝑝
The group velocity of a wave packet is given by 𝑣𝑔 = 𝑣𝑝𝑕 − 𝜆 𝑑𝜆

Case 1. 𝑣𝑔 = 𝑣𝑝𝑕 /2
𝑑𝑣𝑝 1 𝑑𝜆
= This on integration yields ln 𝑣𝑝𝑕 ∞ ln 𝜆 or 𝑣𝑝𝑕 ∞ 𝜆
𝑣𝑝 𝑕 2 𝜆

This implies that the phase velocity is proportional to the square root of the wavelength

Case 2. 𝑣𝑔 = 2𝑣𝑝𝑕
𝑑𝑣𝑝 𝑑𝜆 1
𝑣𝑝 𝑕
= − 𝜆
This on integration yields ln 𝑣𝑝𝑕 ∞ ln λ
or 𝑣𝑝𝑕 ∞ 𝜆−1

This implies that the phase velocity is inversely proportional to the wavelength.

Uncertainty principle

Heisenberg’s analysis of the wave packet revealed the spread

in the estimation of the position and the spread in the
propagation constant of the wave is intrinsically related. A
Fourier transform of the wave functions gives the distribution of
the propagation constant. In summary he product of the The more precisely
standard deviations in the estimates of the position and the the position is determined, the
propagation constant was shown to be greater than or at the
1 less precisely the momentum is
most equal to 2. 𝑖𝑒. , ∆𝑥. ∆𝑘 ≥ 1/2 known in this instant, and vice
This then translates to the standard form of the uncertainty versa.
principle when the propagation constant is transformed to the Heisenberg, uncertainty paper,
momentum through the relation 1927
𝑝 = ℏ𝑘
The position and momentum of a particle cannot be determined simultaneously with unlimited
precision. If one of the parameter is determined with high precision then the other must necessarily
be imprecise, such that the product of the uncertainties is greater than or equal to ℏ/2 ie.,
∆𝑥. ∆𝑝 ≥ ℏ/2
where ∆𝑥 is the uncertainty in the position and ∆𝑝 is the uncertainty in the momentum determined
simultaneously.
The uncertainty relation for energy E and time t for a physical system can be written as
∆𝐸. ∆𝑡 ≥ ℏ/2
Where ∆𝐸 is the uncertainty in the energy E of a system and ∆𝑡 is the uncertainty in the time in which
this energy is estimated.

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In the case of rotational motion the uncertainty relation between the angular position θ and the
angular momentum L can be written as
∆𝜃. ∆𝐿 ≥ ℏ/2
where ∆𝜃 is the uncertainty in the angular position and ∆𝐿 is the uncertainty in the angular momentum
determined simultaneously.

Heisenberg’s Gamma ray microscope:

Heisenberg proposed the gamma ray microscope (as a thought experiment

to illustrate the uncertainty principle) to locate the position of an electron. To
be able to “observe” the electron, it should be “illuminated” by a radiation
whose wavelength is comparable to the size of the scattering object. Hence
it is evident that one should use 𝛾 rays to observe electrons, which in turn
scatter the radiation onto the objective lens of the microscope. In order that
we “see” the electron, the limit of resolution of the microscope should be
comparable to the position uncertainty Δ𝑥.
𝜆
Thus we get Δ𝑥 ≈ sin 𝜃
.

However when the high energy 𝛾 rays can impart momentum to the electrons (following the principles
of Compton Effect).

The maximum momentum imparted to the electron can be estimated from the maximum shift in the
scattered photon momentum. If the momentum of the photons entering the microscope at a half cone
angle 𝜃 is 𝜆 then the maximum momentum gained by the electron in the x direction would be
𝑕
𝑝𝑥 ≈ ± 𝜆 sin 𝜃.

𝑕
Thus the minimum momentum of the electron would be uncertain by a factor ∆𝑝𝑥 ≈ 2 sin 𝜃
𝜆
𝜆 𝑕 𝑕
Thus the product of the uncertainties ∆𝑥. ∆𝑝𝑥 ≈ ∗ 2 sin 𝜃 ≈ 2𝑕 > conforms to the uncertainty
sin 𝜃 𝜆 4𝜋
principle.
This illustrates that in the simultaneous determination of the position and momentum of an electron
results in an inherent uncertainty.

Electron’s existence inside the nucleus

The uncertainty principle can be used to illustrate the impossibilities in physical systems or the
correctness of assumptions. Beta particle emission from radioactive nuclei is one such example.
Experiments show that the beta emission is the emission of an electron with a high energy of about
4MeV by radioactive nuclei. If we assume the electron to be an integral part of the nucleus then we
may be able to estimate the minimum energy of the electron using the uncertainty principle.

If the electron is part of the nuclei, then the position of the electron is uncertain to the extent of the
nuclear diameter. The uncertainty in the position of an the electron
∆𝑥 ≈ 10−14 𝑚
The minimum uncertainty in the momentum of the electron then can be estimated as
ℏ
∆𝑝 = = 5.28 × 10−21 𝑘𝑔𝑚𝑠 −1
2. ∆𝑥

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Hence the minimum momentum of the electron p has to be at least the uncertainty ∆𝒑 and hence

𝑝2 ∆𝑝 2 1 ℏ 2
The kinetic energy of the electron 𝐸 = 2𝑚
= 2𝑚
= 2𝑚 2.∆𝑥
≈ 96 𝑀𝑒𝑉

This implies that the energy of the electron emitted by the radioactive nuclei should be quite high if
electron had to be integral member of the nuclei. Since the energies of the electron emitted by
radioactive nuclei are very less compared to the estimate, we conclude that the electron cannot be a
permanent part of the nuclei, thus illustrating the power of the uncertainty principle.

Conclusions of Unit I

 Brief review of Maxwell’s equations and the concept of EM waves propagating in

free space lead to the conclusion that the energy of EM waves is proportional to the
square of the amplitude of the waves – which does not explain some interactions of
radiation with matter
 The blackbody radiations as due to a cavity of harmonic oscillators to explain the
energy density of radiations by a blackbody was understood. The explanations by
Max Planck on the nature of emission as packets of energy hv – the fundamental
idea of quantization.
 The Dual nature of radiation explains experiments of interaction of radiation with
matter at sub atomic levels. Discussions of the Compton Effect ( relativistic
interactions) to support the dual nature of radiations.
 Dual nature of matter – Louis de Broglie’s hypothesis
 Matter waves – wave packets to represent moving particle – superposition of
waves. Ideas of phase and group velocities of wave packets
 Heisenberg’s Uncertainty Principle – evolution of the uncertainty principle from the
discussion of the wave packet. Implications on physics at small scales.

Some typical solved Numericals

1. Estimate the Compton shift for X rays scattered at 95o with respect to the incident direction. If the
momentum of the scattered X rays is 4.5x10 -24 kg m s-1 estimate the wave length of the incident X Rays.
𝒉
The Compton shift is given by 𝝀𝒇 − 𝝀𝒊 = 𝜟𝝀 = 𝒎 𝟏 − 𝒄𝒐𝒔 𝜽 .
𝒆𝒄

At 95o the shift is 𝜟𝝀 = 𝟐. 𝟒𝟐𝟕 𝒙 𝟏𝟎−𝟏𝟐 ∗ 𝟏 − 𝒄𝒐𝒔 𝟗𝟓 = 𝟐. 𝟔𝟒 𝒙𝟏𝟎−𝟏𝟐 𝒎

𝑕
Wave length of the scattered X ray is 𝝀𝒇 = 𝑝 = 1.472𝑥10−10 𝑚

Wavelength of the incident X ray is 𝝀𝒇 − 𝜟𝝀 = 𝟏. 𝟒𝟒𝒙𝟏𝟎−𝟏𝟎 𝒎

2. In a Compton scattering of electrons with X rays discuss the condition under which the energy gained by
the electron is maximum. If the wave length of the incident X ray is 0.1nm calculate the maximum
energy gained by the electron.
In Compton effect the maximum shift in the wavelength of the scattered X ray is when the angle of
scattering is 180o. At this angle there is a head on collision with the electron and the electron moves
along the incident direction. The momentum and hence the energy transfer is maximum under this
condition.

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The maximum momentum transfer is the maximum momentum loss of the X ray
𝑕 𝑕 𝑕 𝑕
= 𝜆 − 𝜆 ′ = 𝜆 − 𝜆+Δ𝜆 = 3.07 x10-25 Kg m s-1.
The maximum energy transfer is the maximum energy loss of the X ray
𝑕𝑐 𝑕𝑐 𝑕𝑐 𝑕𝑐
= − = − = 575.16eV
𝜆 𝜆′ 𝜆 𝜆+Δ𝜆

3. Estimate the energy of a non relativistic electron if it to confined in a region of width 10 -14 m and
calculate the de Broglie wavelength of the electron with this energy. Comment on the results obtained.

The position of the electron is uncertain to the extent of 10-14 m. ∆𝒙 ≈ 𝟏𝟎−𝟏𝟒 𝒎

ℏ
The minimum uncertainty in the momentum ∆𝒑 = 𝟐.∆𝒙
= 𝟓. 𝟐𝟕 × 𝟏𝟎−𝟐𝟏 𝒌𝒈𝒎𝒔−𝟏 =p

𝒑𝟐 ∆𝒑𝟐 𝟏 ℏ 𝟐
The kinetic energy of the electron 𝑬 = = = ≈ 𝟗𝟔 𝑴𝒆𝑽
𝟐𝒎 𝟐𝒎 𝟐𝒎 𝟐.∆𝒙
𝒉
𝝀= 𝒑
= 𝟏. 𝟐𝟓𝟕 𝒙 𝟏𝟎−𝟏𝟑 𝒎.

The de Broglie wavelength > the width of the region, which implies the electron cannot be confined in
this interval.
4. Find the spread in the wavelength of a photon whose life time in the excited state is uncertain to 10-10s
if the wavelength of emission is 541nm.

The uncertainty relation for energy E and time t for a physical system can be written as
∆𝐸. ∆𝑡 ≥ ℏ/2 where ∆𝐸 is the uncertainty in the energy E of a system and ∆𝑡 is the uncertainty in
the time in which this energy is estimated.

𝑐 ∆𝜆 ℏ
∆𝐸. = ∆𝑕𝜈 = 𝑕∆ = 𝑕𝑐. 2 =
𝜆 𝜆 2∆𝑡
𝜆2
∆𝜆 = = 7.76 𝑥 10−14 𝑚
4𝜋𝑐 ∆𝑡

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Numericals

1. Find the de Broglie wavelength of electrons moving with a speed of 107 m/s (Ans 7.28 x 10-11 m)
E1 = h² / (2 λ² m) 2. Compare the momenta and energy of an electron and photon whose de Broglie wavelenth is
E2 = 2 m c λ / h 𝒉
650nm (Ans Ratio of momenta =1; ratio of energy of electron to energy of photon =𝟐𝒎𝝀𝒄 = 𝟏. 𝟖𝟔𝟕𝒙𝟏𝟎−𝟔 )
3. Calculate the de Broglie wavelength of electrons and protons if their kinetic energies are
i) 1% and ii) 5% of their rest mass energies. (Ans Rest mass energy of electron = 8.19x 10-14 J; rest
-10 𝒉
mass energy of protons = 1.503 x 10 J. The de Broglie wavelength 𝝀 = Electron 1%
𝟐𝒎𝑬
𝝀 = 𝟒. 𝟎𝟎𝒙𝟏𝟎−𝟏𝟑 𝒎 Electron 5% 𝝀 = 𝟏. 𝟕𝟗𝒙𝟏𝟎−𝟏𝟑 𝒎 Proton 1% 𝝀 = 𝟐. 𝟏𝟕𝒙𝟏𝟎 −𝟏𝟔
𝒎 Proton 5% 𝝀 =
𝟗. 𝟕𝟐𝒙𝟏𝟎−𝟏𝟕 𝒎)
4. An electron and a photon have a wavelength of 2.0 A. Calculate their momenta and total
energies.
5. What is the wavelength of an hydrogen atom moving with a mean velocity corresponding to
𝒉
for Electron, h^2/2mlambda^2 the average kinetic energy of hydrogen atoms under thermal equilibrium at 293K? ( 𝝀 = 𝟑𝒎𝒌𝑻 =
For Photon, hc/lambda

𝟏. 𝟒𝟕𝒙𝟏𝟎−𝟏𝟎 𝒎 )
6. The frequency of Surface tension waves in shallow water is given by ν= (2πT/ρλ 3)½, where T
is the surface tension, ρ is the density of the medium and λ the wavelength of the waves. Find
the group velocity of the waves.
7. The relation between the wavelength λ and frequency ν of electromagnetic waves in a wave
guide is given by λ=c/√(ν2 - νo2). Find the group velocity of the waves.
8. The speed of an electron is measured to be 1 km/s with an accuracy of 0.005%. Estimate the
uncertainty in the position of the particle.
9. The spectral line of Hg green is 546.1 nm has a width of 10-5 nm. Evaluate the minimum time
spent by the electrons in the upper state before de excitation to the lower state.
ℏ 𝝀𝟐
(Ans: ∆𝒕 = = = 𝟕. 𝟗𝟏𝒙𝟏𝟎−𝟗 𝒔 )
𝟐.∆𝑬 𝟒𝝅𝒄𝚫𝝀

10. The uncertainty in the location of a particle is equal to it's de Broglie wavelength. Show that
the corresponding uncertainty in its velocity is approx one tenth of it's velocity. (Ans: ∆𝒑 =
ℏ 𝒉 𝒑 𝒗 𝒗 𝒗
= = Hence ∆𝒗 = = ≈ )
𝟐.∆𝒙 𝟒𝝅𝝀 𝟒𝝅 𝟒𝝅 𝟏𝟐.𝟓𝟔 𝟏𝟎
11. Determine the maximum wavelength shift in the Compton scattering of photons from protons.
(Ans = 2.64×10−5 Å)
𝜆2
12. Show that for a free particle the uncertainty relation can also be written as ∆𝑥. ∆𝜆 = | 4𝜋 |
where Δx is the uncertainty in location of the wave and Δλ the simultaneous uncertainty
in wavelength.

https://www.youtube.com/watch?v=yy6TV9Dntlw

https://www.youtube.com/watch?v=EA-wcFtUBE4

https://www.youtube.com/watch?v=vkVnnN0MjIE

https://www.youtube.com/watch?v=cugu4iW4W54

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