Module 3: Elements of Quantum Mechanics (6 h)

➢ Introduction / Need for quantum mechanics

➢ Idea of quantization (Planck & Einstein) - Compton effect
➢ De Broglie hypothesis – Davisson – Germer Experiment
➢ Wave function and probability interpretation
➢ Heisenberg uncertainty principle
➢ Schrodinger wave equation (time dependent & time independent
 Quantum nature of radiation
1st evidence from spectrum emitted by a black-body

What is a black body ?

What is a white body?

An object that absorbs all incident radiation, i.e. no reflection - black body

An object that reflects all incident radiation, i.e. no absorption – white body.

A black body is a theoretical object that absorbs 100% of the radiation that hits it.
Therefore it reflects no radiation and appears perfectly black.

In practice no material has been found to absorb all incoming radiation .

 A black-body?
(An object that absorbs all incident radiation, i.e. no reflection)

A small hole cut into a cavity is the most popular

and realistic example.
None of the incident radiation escapes

What happens to this radiation?

•The radiation is absorbed in the walls of the cavity

•This causes a heating of the cavity walls
•Atoms in the walls of the cavity will vibrate at frequencies characteristic of
the temperature of the walls
•These atoms then re-radiate the energy at this new characteristic frequency

The emitted "thermal" radiation characterizes the equilibrium

temperature of the black-body
 A black-body reaches thermal equilibrium when the
incident radiation power is balanced by the power re-
radiated, i.e. if you expose a black-body to radiation, its
temperature rises until the incident and radiated powers
balance.
The maximum wavelength emitted by a black body
radiator is infinite. It also emits a definite amount of energy
at each wavelength for a particular temperature, called
black body radiation curves,. All objects emit radiation
above absolute zero.
• The emission from a black-body depends only on its
temperature.

• Objects at 300 K radiate in the infrared.

•Objects at 600 - 700 K start to glow.
•At high T, objects may become white hot
Black-body spectrum This graph shows how the black
body radiation curves change at
various temperatures.
All these have their peak
wavelengths in the infra-red part
of the spectrum as they are at a
relatively lower temperature

As the temperature increases, the

peak wavelength (not peak
intensity) emitted by the black body
decreases.
ie. as the temperature increases
from 1250 to 2000K, the peak
wavelength decreases from
2.5um(2500nm) to 1.5um (1500 nm)

Fig : Black body radiation curves showing peak wavelengths at various temperatures
A black-body at room temperature appears black, as most
of the energy it radiates is infra-red and cannot be
perceived by the human eye.

At higher temperatures, black bodies glow with increasing

intensity and colors that range from dull red to blindingly
brilliant blue-white as the temperature increases.
LAVA flow

One can measure the

temperature of the lava
using the colour.
 19th century a major problem for physicists : To predict the intensity of
radiation emitted by a black body at a specific wavelength.

Wien’s theory : Predicted the overall form of the curve by treating the
radiation as gas molecules.

Draw back: However, at long wavelengths his theory disagreed with

experimental data.

Rayleigh and Jeans : Later given a formula by considering the radiation

within the black body cavity to be made up of a series of standing waves.

They thought that electromagnetic radiation was emitted by oscillating atoms

in the walls of the black body and this radiation set up a standing wave
between the walls. Their formula stated: as given ……………

Wien, Rayleigh-Jeans and Planck distributions

8 k BT e −  / T 8 hc
uRJ (  ) = ; uW (  )  ; uP (  ) =
 4 5  5 ( ehc /  kBT − 1)
Draw backs : For large wavelengths it fitted the experimental data but it had
major problems at shorter wavelengths.
As the wavelength tended to zero, the curve would tend to infinity.
However we know that there is a peak wavelength for each temperature,
and the energy emitted at either side of this peak dropped.
The Rayleigh-Jeans Law predicted no peak wavelength.
Ultraviolet catastrophe
The formulae failed to explain and account for energy outputs at short
wavelengths (the ultraviolet wavelengths) known as the ultraviolet
catastrophe.
The failure of Rayleigh – Jeans law is known as the ultraviolet catastrophe.
 Comparison between Classical and
Quantum viewpoint

There is a good fit at long wavelengths, but at short

wavlengths there is a major disagreement.
Rayleigh-Jeans ∞, but Black-body 0.
Max Planck

The law was the first to accurately describe black body radiation,
and resolved the ultraviolet catastrophe. It is a breakthrough in
modern physics and quantum theory.

A major breakthrough was made by Max Planck who made a

formula that agreed with experimental data.

In 1900, Max Planck studied black body radiation from the

standpoint of thermodynamics.

He proposed that the energy of each electromagnetic oscillator is

limited to discrete values and cannot be varied arbitrarily, contrary
to the assumptions of classical physics.
This limitation of energies to discrete values is called the
quantization of energy.

Planck corrected the problem by assuming that only

specific energies hν could be involved. These permitted
energies of an electromagnetic oscillator are integer
multiples of hν

E = nhν ; n = 0, 1, 2, ……….

where h is Planck’s constant. On the basis of this

assumption, Planck was able to derive the Planck’s
Distribution, which fit the experimental data well at all
wavelengths
Before Planck it was assumed that these could have any
value of energy,

but

Planck decided that the energy must go up in discrete

amounts (quantized) because the frequencies of the
oscillating electrons could only take certain values.

As energy is proportional to frequency (E = hν) , where h is

the Planck constant 6.626 x 10-34 Js) if frequency can only
take discrete values, this means that energy is also
quantized.

The electrons have a fundamental frequency (like standing

waves on a string) and the frequency can only go up in
whole multiples of this frequency, called the quantum
number. This assumption led Planck to correctly derive his
formula.
Application for Black Body
Limitations of Classical theory (failures)

1. Black body radiation

2. Origin of discrete spectra of atoms (gases)
3. Variation of specific heat of metals and gases
4. Stability of atoms
5. Failed to explain photoelectric effect, Compton effect,
Zeeman effect, Raman effect, etc….
Quantization is the procedure of constraining
something from a continuous set of values (such as the
real numbers) to a relatively small discrete set (such as
the integers).

In Physics, quantization is the process of transition

from a classical understanding of physical phenomena
to a newer understanding known as “ quantum
mechanics".
 Quantum Mechanics

Quantum mechanics is a physical science dealing with

the behaviour of matter and energy on the scale of atoms
and subatomic particles / waves.
 Planck’s Radiation Formula

In 1900 Planck explained the experimentally observed distribution of energy in the spectrum
of black body and suggested that the correct results can be obtained if the energy of
oscillating electrons is taken as discrete rather than continuous.
He derived the radiation law by using the following assumptions:
1. A chamber containing blackbody radiations also contains simple harmonic oscillators of
molecular dimensions which can vibrate with all possible frequencies.
2. The frequency of radiation emitted by an oscillator is the same as the frequency of
vibration.
3. An oscillator cannot emit energy in a continuous manner, it can emit energy in the
multiples of a small unit called quantum (photon). If an oscillator is vibrating with a
frequency ‘ν’, it can radiate in quantas of magnitude hν; the oscillator can have discrete
energies values En given by En= nhν ; where n – an integer; h – Plancks constant
(6.625 x 10-34 Joule- sec)
4. The oscillators can emit or absorb radiation energy in packet of hν. (revolutionary
assumption)
This implies that the exchange energy between radiation and matter cannot take place
continuously but are limited to discrete set of values 0, hν, 2hν, 3hν, ……….nhν.
Planck's radiation formula in terms of frequency

Planck's radiation formula in terms of wavelength

 THEORY

• It was thought that light had a wave nature.

• Phenomena such as interference, diffraction and

polarisation can be explained only on the basis of
wave nature of light.

• At the same time, phenomena such as photo

electric effect and compton effect, etc could not
be explained by the wave nature of light.

• The theory behind the Compton Effect was to

prove that light has a particle nature also.
 Compton effect
Experiment revealing the particle nature of X-ray (radiation, with wavelength ~ 10-
10 nm)

Compton, Arthur Holly (1892-1962),

American physicist and Nobel laureate
whose studies of X-rays led to his discovery
in 1922 of the so-called Compton effect.

The phenomenon in which the wavelength of

the scattered X-rays is greater than the
wavelength of the incident X-rays is called
Compton Effect. The difference in
wavelength is known as Compton shift.
The Compton effect is the change in
wavelength of high energy electromagnetic
radiation when it scatters off electrons.
The discovery of the Compton effect confirmed that electromagnetic
radiation has both wave and particle properties, a central principle of
quantum theory.
Compton scattering is an inelastic scattering of a photon by a free charged
particle, usually an electron.
Compton scattering is an example of inelastic scattering, because the wavelength of
the scattered light is different from the incident radiation
The phenomenon in which the
wavelength of the scattered X-
rays is greater than the
wavelength of the incident X-
rays is called Compton Effect.
The difference in wavelength is
known as Compton shift.
The value of Compton shift is
dependent on the angle of
scattering.

The greater the angle of scatter, the more energy is lost by the
photon h
 − =
'
(1 − cos  )
mo c
Experimental Demonstration of Compton Effect
A beam of X-rays falls on the target (graphite).
Detector capable of moving in an arc, measures the energy of the scattered
X-rays at various angles of θ.
The graphs show the Compton experimental results.
For each angle other than 0o, two peaks appear.
Wavelength of 1st peak matches with the original (incident ) wavelength. This
corresponds to the photon that gets scattered from the tightly bound electrons of
the graphite. Hence they don’t lose their energy.
Wavelength of the second peak corresponds to the scattered photon due to
loosely bound electron in the graphite, where they lose some amount of energy.

Compton performed the experiment with gamma rays and also found that there
was no change in Compton shift, proving that Compton shift does not depend on
the incident wavelength.
 Beam of x-ray with sharp wavelength 
falls on graphite target. For various angle
q the scattered x-ray is measured as a
function of their wavelength

Although initially the incident beam

consists of only a single well-defined
wavelength () the scattered x-rays have
intensity peaks at two wavelength (’ in
addition), where ’ > .

Unexplained by classical
wave theory for radiation

Wavelength No shift of wavelength is

shift predicted in wave theory
of light
Wave nature

We regard EM waves as WAVES because under suitable circumstances they

exhibit
1) Diffraction
2) Interference
3) Polarization

Particle nature

Similarly other circumstances they behave as though they consist of stream

of PARTICLES
1) Photoelectric effect
2) Compton effect.

Thus radiation or light waves has dual nature (both wave and
particle nature)
 Idea of Quantization (Planck and Einstein)

The properties of blackbody radiation, the radiation emitted by hot objects,

could not be explained with classical physics.

Max Planck postulated that energy was quantized and could be emitted or
absorbed only in integral multiples of a small unit of energy, known as a
quantum.
The energy of a quantum is proportional to the frequency of the radiation; the
proportionality constant h is a fundamental constant (Planck’s constant).

Albert Einstein used Planck’s concept of the quantization of energy to explain

the photoelectric effect, the ejection of electrons from certain metals when
exposed to light.

Einstein postulated the existence of what today we call photons, particles of

light with a particular energy, E = hν.

Both energy and matter have fundamental building blocks: quanta and atoms,
respectively.
As can be showed in figure, a minimum energy of 2.0 eV is required to eject a
photon off of potassium, and so red light would not work, while green and purple
would.

Fig. : Potassium requires 2.0 eV to eject an electron, and a photon of red light (700
nm) only has 1.77eV and so no matter intense the red light is, it can not kick of an
electron.

Green and purple light have more energy, and when you shine them on the
potassium you can kick off an electron.
Louis de Broglie
• 1892 – 1987
• French physicist
• Originally studied history
• Was awarded the Nobel
Prize in 1929 for his
prediction of the wave
nature of electrons

de Broglie (1924) made a great unifying, speculative hypothesis that just

as radiation has particle-like properties, electrons and other material
particles possess wave-like properties.

For free material particles, de Broglie assumed that the associated wave
also has a frequency and wavelength related to its energy E and
momentum p
Nature loves symmetry
The concept of dual nature of radiation prompted Louis de Broglie to suggest the
idea of matter waves.

In 1924, his suggestion was based on the following facts

1. Nature loves symmetry (nature is symmetrical)

2. The entire universe consists of radiation (energy) and matter only

Therefore the two physical entities ie. matter and energy must be symmetrical .

ie. to say, if radiant energy has dual characterization, matter must also have dual
(particle like and wave like) nature.

So a moving particle is associated with a wave known as matter wave or pilot

wave or de Broglie wave.

(symmetry : two halves of an object are exact mirror images of each other)

λ = h/p
Properties of MATTER WAVES.
1. Lighter is the particle, greater is the wavelength associated with it.
2. Smaller is the velocity of the particle, greater is the wavelength associated with
it.
3. Matter waves are not electromagnetic waves.
4. Matter waves are generated by the motion of particles. If the particles are at
rest, then there is no meaning of matter waves associated with them.
5. The wavelength of the matter waves are independent of charges on the
particles, but depends upon the velocity of particle.
6. These waves can travel faster than the velocity of light.
7. The velocity of the matter waves is not constant as that of E-M radiation. It
depends on the velocity of the material particle.
8. The only function of the wave is to pilot or to guide the matter particles as
shown and hence it is called as pilot wave.

9. The matter wave is not a physical phenomenon. It is rather a symbolic

representation of what we know about the particle. It is a wave of probability.
Davisson and Germer Experiment
This experiment performed in 1927 confirmed the de Broglie hypothesis.
Ie. To prove the hypothesis that particles of matter such as electrons have
wave like properties.
The experiment not only played a major role in verifying the de Broglie
hypothesis and demonstrated the wave-particle duality, but also was an
important historical development in the establishment of quantum mechanics
and Schrodinger equation
• Electrons were directed onto nickel
crystals
• Accelerating voltage is used to control
electron energy: E = |e|V
• The scattering angle and intensity
(electron current) are detected
– φ is the scattering angle

https://www.youtube.com/watch?v=Ho7K27B_Uu8
The maximum interference is due to constructive interference , a
phenomenon confined only to waves.
Davisson and Germer Experiment
• Observations:
• Current vs accelerating
voltage has a maximum,
i.e. the highest number
of electrons is scattered
in a specific direction
• This can’t be explained
by particle-like nature of
electrons  electrons
scattered on crystals
behave as waves

For φ ~ 50° the maximum is at ~54V

 When accelerated at different voltages……………..

The peak indicates the wave nature of electrons.

nλ = 2d Sin (90 – θ/2) (θ = 50o)
1. X-ray of wavelength 0.240 nm are Compton scattered and scattered beam is
observed at an angle 60o relative to the incident beam. Find the wavelength of the
scattered X-rays.

2. A beam of X-rays is scattered by a target. At 45o from the beam direction the scattered
X-rays have wavelength of 2.2 pm. What is the wavelength of X- rays in the direct
beam?

3. At what scattering angle will incident 100 keV X-rays leave a target with an energy of
90 keV?
 The more precisely the position is
determined, the less precisely the
momentum is known in this instant,
and vice versa.

--Heisenberg, uncertainty paper, 1927

• In quantum physics, the Heisenberg uncertainty principle states that certain
pairs of physical properties like position and momentum cannot both be known
to arbitrary precision. I.e.. More precisely one property is known, the less
precisely the other can be known.
• It is impossible to measure simultaneously both position and velocity of a
microscopic particle with any degree of accuracy or certainty.
• In quantum mechanics a particle is described by a wave. The position is where
the wave is concentrated and the momentum is the wavelength. The position is
uncertain to the degree that the wave is spread out and the momentum is
uncertain to the degree that the wavelength is ill- defined.
• “It is impossible to know both the exact position and exact momentum of an
object at the same time”.
The Heisenberg uncertainty principle states that in an simultaneous
determination of a pair of physical quantities which describes the motion
of an atomic particle , the product of uncertainties is equal to
As a result it is impossible to design an experiment to prove the wave and particle
nature of matter at the same time.

If one measures the position accurately, then the measurement of momentum

becomes incorrect and vice versa.

The principle can also be written as

or

or the errors in the measurement of energy and time respectively

1. The position and momentum of 2 KeV electrons are measured
simultaneously. If its position is located to within 1Å, what is the
percentage of uncertainty in its momentum?

2. The life time of an energy state is 10-8 s, calculate the uncertainty in the
frequency of the photon emitted during the transition (de-excitation of
the atom).
 Wave function and probability interpretation

Wave function, in quantum mechanics, variable quantity that mathematically describes the wave
characteristics of a particle.
(or)
A wave function (Ψ) is a mathematical function that relates the location of an electron at a given
point in space (identified by x, y, and z coordinates) to the amplitude of its wave, which
corresponds to its energy. Thus each wave function is associated with a particular energy E.

Properties of wave functions

• A wave function uses three variables to describe the position of an electron

A fourth variable is usually required to fully describe the location of objects in motion.
Three specify the position in space (as with the Cartesian coordinates x, y, and z), and one
specifies the time at which the object is at the specified location.
• The magnitude of the wave function at a particular point in space is proportional to the amplitude of the
wave at that point.

Many wave functions are complex functions, which is a mathematical term indicating that they contain
−1, represented as i . Hence the amplitude of the wave has no real physical significance.

• The square of the wave function at a given point is proportional to the probability of finding an electron
at that point, which leads to a distribution of probabilities in space.
The square of the wave function ( Ψ2 ) is always a real quantity [ −1 2=−1 ] is proportional to the probability of
finding an electron at a given point. More accurately, the probability is given by the product of the wave function
Ψ and its complex conjugate Ψ*, in which all terms that contain i are replaced by −i .
We use probabilities because, according to Heisenberg’s uncertainty principle, we cannot precisely specify the
position of an electron. The probability of finding an electron at any point in space depends on several factors,
including the distance from the nucleus and, in many cases, the atomic equivalent of latitude and longitude.
• Describing the electron distribution as a standing wave leads to sets of quantum numbers that are
characteristic of each wave function

• Each wave function is associated with a particular energy

 Physical significance of Ψ

1. It relates the particle and wave nature of matter statistically.

2. It is a complex quantity and hence we cannot measure it. It shall be expressed of
the form  ( x, y , z , t ) = a + ib (1)
where ‘a’ and ‘b’ are real functions of variables (x,y,z,t)
The complex conjugate of Ψ is denoted by Ψ* by changing ‘i” to ‘-i’
  ( x, y, z, t ) = a − ib (2)
multiplying (1) and (2)
( x, y, z, t )  ( x, y, z, t ) = a 2 + b 2 (3)

The product (LHS)    is denoted by P

Ie. P = ( x, y, z, t )  ( x, y, z, t ) = ( x, y, z, t )
2

 ( x, y , z , t ) = a 2 + b 2
2
(4)

3. Its square is a measure of the probability of finding the particle at a particular

position . It cannot predict the exact location of the particle
 ( x, y , z , t )
2
is called probability density
4. For the motion of a particle, the probability of finding the particle in a
volume element ‘dv’ is
Pdv = ( x, y, z, t )  ( x, y, z, t )dv
=  ( x, y, z, t ) dv
2

For the motion of the particle in one dimension, Pdx = ( x, t ) = ( x, t ) 2 dx

probability per unit

 distance
Px =  ( x, t ) dx
2
Therefore , the total probability is
−

For 3-dimensional space P =  ( x, y, z, t ) dv
2

−

5. The normalising condition for the wave function for the motion of
a particle in 3-dimension is 

  dv = 1 (7)
2
( x, y , z , t )
−

Where Ψ is the function of space coordinates (x,y,z)

6. If the wave function does not satisfy the normalization condition eqn (7), then
it must be multiplied by a constant factor called normalization factor.
For eg.
 dx = N
 ( N 1 )
2

1
The normalization factor will be and the normalized wave function
will be 1  N
N

7. The wave function Ψ must approach zero as ‘x’ tends to ±α.

8. The wave function satisfying the following condition is said to be an

orthogonal wave function
  j ( x)dx = 0

i
−

The orthogonality condition guarantee the non-interference of the

wave function representing different states.
9. Degeneracy

If Ψi and Ψj corresponds to the same energy “E” then this is called as degenerate
state.
6. If the wave function does not satisfy the normalization condition eqn (7), then
it must be multiplied by a constant factor called normalization factor.
For eg.
 dx = N
 ( N 1 )
2

1
The normalization factor will be and the normalized wave function
will be 1  N
N

7. The wave function Ψ must approach zero as ‘x’ tends to ±α.

8. The wave function satisfying the following condition is said to be an

orthogonal wave function
  j ( x)dx = 0

i
−

The orthogonality condition guarantee the non-interference of the

wave function representing different states.
9. Degeneracy

If Ψi and Ψj corresponds to the same energy “E” then this is called as degenerate
state.
10. Orthonormal set: The normalization and orthoganility conditions may be
combined as follows

i= j
 i  j dv = 1


=0 i j (10)

Wave function of the form eqn (10) is said to be orthogonal wave function.

11. Ψ must be finite for all values of x,y,z.

12. Ψ must be well behaved i.e single valued and continuous every where.
13. Ψ must be continious in all regions except in those region where the
potential energy V(x,y,z) = α
 Schrodinger Wave Equation

Schrodinger wave equation is a mathematical expression describing the energy and position of the
electron in space and time, taking into account the matter wave nature of the electron inside an atom.

Schrodinger wave function

Second 𝜕2𝜓 8𝜋2𝑚

derivative w.r.t “x” + (E-V) 𝜓 = 0
𝜕𝑥2 ℎ2

T. E P. E
Position

𝜕2𝜓
If ℏ =
𝒉
𝟐𝝅 + 2𝑚
ℏ
(E-V) 𝜓 = 0
𝜕𝑥2 2
• The Schrödinger equation is one of the basic equation in quantum mechanics like Newton’s
law of motion.
• Newton’s law of motion is applied only to macroscopic particles, whereas Schrödinger
equation is used for both macroscopic and microscopic particles.
• Schrödinger derived a mathematical equation to describe the dual nature of the matter waves.
There are two forms of Schrödinger wave equation
i) Time dependent wave equation
ii) Time independent wave equation
• He derived the equation incorporating the following assumptions:
i) de Broglie wavelength can be applied for the matter waves for any field of force. Based on
this, the total energy of a particle can be written as, TE = PE + KE
𝑃2
(or) E = V + ½ mv2 (or) E = V + 2𝑚
(1)

Rearranging P= [2m(E-V)]½ (2)

But from the de Broglie wavelength we have,
ℎ
𝜆=
𝑝
Sub (2) in above equation

ℎ
𝜆= (3)
[2m(E−V)]½

ii) The wave function associated with the particles, with function of time can be written as,

𝜓 = 𝜓0 𝑒 −𝑖𝜔𝑡 (4)

Where 𝜓0 is the amplitude of the wave at the point (x, y, z) and ω = 2πυ, where υ is the frequency of the
radiation and ω is angular frequency.