Deals with smaller Failure of classical

particles mechanics
Atoms, molecules, electrons, Classical mechanics failed to
protons etc. explain many observed properties
of matter. Eg., black body
radiation, photoelectric effect.

Hypothesis of Answers the

quanta inconsistencies in
Radiation is emitted or
absorbed by matter in discrete
Newton’s mechanics
packets called quanta.
 BLACKBODY RADIATION THEORY

• Blackbody is an ideal body which absorbs all incident EM waves

regardless of its frequency and incident angle.
• It is a perfect absorber of light.
• Reflectivity R = 0 and Transmitivitty T = 0
• Practically no perfect blackbodies exist.
• All bodies are approximated as blackbody and behavior of
bodies are studied comapared to blackbody.
• When bodies heated using radiation- atoms absorb energy
and the charged particles inside the atom starts vibrating
which in turn causes emission of energy.

• When high energy radiations are given to a black body- it

absorbs all the radiations, they moves from their
stable/ground state energy to higher energy levels.

• They emit this energy and try coming back to ground state
energy level.
 EXPERIMENTAL RESULTS

• Experiments with
approximated
blackbodies were done to
see how EM wavevs are
emitted.
 Results showed:

• Intensity of light emitted by a blackbody is

high at a particular wavelength at a
particular temperature.
• For all other wavelength, light is emitted
at a lower intensity.
• Peak wavelength get left shifted with
increase in temperature.
 Theoretical explanations
Wien’s explanations, Rayleigh’s explanation and Planck’s
explanations for blackbody
 Wein’s explanation for blackbody
spectrum

Wein used some classical thermodynamical arguements to

explain blackbody spectrum and obtained mathematical
expression connecting intensity of light emitted and wavelength.
𝟖𝝅𝒉𝒄 − 𝒉𝒄
𝒖𝝀 𝒅𝝀 = 𝟓
𝒆 𝝀𝑲𝑻 𝒅𝝀
𝝀

This mathematical expression gives low intensity for was in

accordance to blackbody spectrum for the lower wavelength
region, but couldnt explain the higher wavelength region.
 Rayleigh’s explanation for blackbody
spectrum
Rayleigh used classical electromagnetic theory to explain
blackbody spectrum and obtained mathematical expression
connecting intensity of light emitted and wavelength.
𝟖𝝅𝑲𝑻
𝒖𝝀 𝒅𝝀 = 𝒅𝝀
𝝀𝟒

This mathematical expression was in accordance to blackbody

spectrum for the high wavelength region, but couldnt explain the
low wavelength region.
 PLANCK’S THEORY

• Rayleigh and Wein were assuming the classical nature of

EM radiation where EM radiations were considered as
waves.
• With the failure of explaining blackbody with classical theory
Planck introduced a revolutionary theory of EM radiations
that EM radiations shows particle nature.
• This was the beginning of Quantum mechanics and modern
physics.
• According to Planck light consists of minute particles that
have properties of waves that are associated with them.
• Each particle/quanta of energy of the light is called
photons.
• Each photon has an energy equal to hʋ where h is called
planck’s constant and ʋ is the frequency of the light.
With these theorotical assumptions he developed a mathematical
expression for the blackbody spectrum connecting intensity and
wavelength, which takes the form,
𝟖𝝅𝒉𝒄 𝟏
𝒖𝝀 𝒅𝝀 = 𝒉𝒄
𝒅𝝀
𝝀𝟓
𝒆𝝀𝑲𝑻 −𝟏

This mathematical expression was well accordance with the

blackbody spectrum both in low and high wavelength region.
Success of Planck’s new theory where EM radiations were
considered as quantas of energy was thus became largerly
accepted Quantum mechanics.
Planck’s equation converges to Wein’s law at low
wavelength region and to Rayleigh’s law at high wavelength
region.
ℎ𝑐
For low wavelength, 𝑒 𝜆𝐾𝑇 >> 1 and hence it converges to
Wien’s law.
ℎ𝑐
For high wavelength, 𝑒 𝜆𝐾𝑇 <<1 and hence converges to
Rayleigh’s law.
 BLACK BODY AS QUANTUM
MECHANICAL OSCILLATOR
• Planck considered blackbody as a system of quantum
oscillators.
• Each atom in the system will be acting as an oscillator.
• According to Planck, atoms in a system are confined to a small
region and this confinement results in discretization of energy
levels.
• Atoms will be able to absorb the energy coming from the
incoming EM radiation in quantized form and oscillations of
atoms happens between these energy levels.
• With these approximations, he was able to explain the blackbody
curve perfectly.
• But he failed to explain or prove why energy is getting quantized
with size confinement.
• Blackbody spectrum act as response curve of quantum
mechanicl oscillator.
• Whenever the incident radiation has a freuency equal to
natural frequency of the blackbody, atoms makes oscillations
and emits maximum radiation at that particular frequency.
• Natural frequency of the blackbody depends on its
temperature.
• When temperature of the body increases, natural frequency of
the body also increase. That is why the blackbody spectrum
shifted to higher frequency when temperature is increasing.
 SEED IDEAS
1. Any material has a unique system of energy levels at its
core, which can act as a source of light either spontaneously or
upon excitation.
2. Radiations are emitted from the core of matter due to the de-
excitation of quantum mechanical particles between energy
levels.
3. Quantum mechanical transitions within a material can
produce a spectrum of photons.
4. Different colours of light emanating from a material are
characteristic of its internal electronic structure.
 EXPERIMENTAL EVIDENCE FOR
QUANTUM THEORY: PHOTOELECTRIC
EFFECT
• Experimental evidence provided
by Einstein.

• When light trikes on a metal

surface, electrons are ejected
from the surface of the metal and
movement of electrons produces
a current if it is connected to a
circuit.
• The photons with energy hʋ strikes on the metal surface and
this energy absorbed by the electron utilizes it in two ways: To
eject the electron from the metal by breaking the bond and
for further movement of electrons after being ejected.

• The energy required to eject electron from the metal by

breaking the bond - work function of the metal(𝜙0 = ℎ𝜐0 ).

• The energy required for the further movement of electron -

Kinetic energy of the moving electron.
Experimental results:

• The maximum kinetic energy of the ejected electrons is

independent of the intensity of the light, but is proportional to
the frequency of the light.
• There is a minimum threshold frequency of light below which
no electrons are ejected.
• The photoelectric effect is instantaneous, meaning that
electrons are ejected as soon as the light strikes the material.
Wave nature of particles: Matter waves
• De-Broglie’s dual nature of matter : Matter exhibits dual nature -
wave and particle nature.
• De-Broglie suggested that wavelength asociated with any
𝒉
matter is given by λ =
𝒑
where p = mv, h = 6.625x10-34Js(Planck’s constant)
𝒉
𝝀 =
𝒎𝒗
Wavelength of a ball of mass Wavelength of an electron
100g moving with a speed of moving at a speed of
10m/s is 107m/s is
−
34
− ℎ 6.625×10
ℎ 6.625×10 34 λ= = −
λ= = 𝑚𝑣 9.1×10 31
×107
𝑚𝑣 0.1×10 − 11
− 34 = 7.280 × 10 m
= 6.625 × 10 𝑚
This is comparable to the size
The wavelength is so small of the atoms. Hence cannot be
that we are unable to ignored.
measure.
• Although the dual nature of matter is applicable to all material
objects, it is significant for microscopic bodies only.
• In a wave, there is something that varies periodically.
• in water waves - height of the water surface varies.
• in sound waves - pressure varies.
• in light waves - electric and magnetic fields varies.
• The quantity whose variations make up matter waves is called
the wave function, denoted by ψ.
• ψ is a mathematical function which describes the state of a
particle or a system.
 Characteristics of wavefunctions
• It is a function of position co-ordinate and time.
• It is generally a complex function.
• Eg., ψ = 𝐴𝑒 −𝑖𝜔𝑥𝑡
• Finite and should tend to zero when x tends to ∞.
• ψ(x) should be single valued and continous at all points.
𝜕𝜓 𝜕2𝜓
• ψ(x), , 2 etc should be continous and single valued at
𝜕𝑥 𝜕𝑥
all points.
 Probability interpretation of wave function
• ψ*ψ or |ψ|2 represents the probability density or the
probability of finding the particle in unit volume.
• If a particle exist in a given region of space, the total
probability of finding the particle in that region is one.
∗
Mathematically, ∫𝛹 𝛹𝑑𝑣 = 1 - Normalization condition.
• If a particle doesnot exist in a given region of space, the
total probability of finding the particle in that region is zero.
ψ itself has no physical signficance or is not observable.
But ψ*ψ gives the probability of finding the particle in a
region and is observable.
 THE SCHRODINGER
EQUATIONS
• Time dependent schrodinger equations
• Time independent schrodinger equations
Time dependent schrodinger equations
• This is the most fundamental equation of quantum mechanics.
• The differential equation for a wave associated with a particle and
propogating along the x direction may be written as,
𝜕2𝛹 1 𝜕2𝛹
2
= 2 2
𝜕𝑥 𝑣 𝜕𝑡
Solution to this equation takes the form,
−𝑖
(𝐸𝑡−𝑝𝑥)
𝛹= 𝑎𝑒 ℏ ----------(1)

29
• Total energy E of the particle is sum of KE and PE,
𝑝2
E= +V
2𝑚
𝑝2𝛹
multiplying with 𝛹 ⇒ E𝛹 = +V𝛹 --------(2)
2𝑚
• differentiating (1) wrt to ‘t’,
𝜕𝛹 −𝑖𝐸
= 𝛹
𝜕𝑡 ℏ
𝜕𝛹
E𝛹 = iℏ ---------(3)
𝜕t
• differentiating (1) wrt ‘x’ twice,
𝜕2𝛹 −𝑝2
= 𝛹 ---------(4)
𝜕𝑥2 ℏ2
• Substituting E𝛹 and p2𝛹 from (3) and (4) in (2), we get,
𝜕𝛹 −ℏ2 𝜕2𝛹 + 𝑉𝛹
iℏ = --------------(5)
𝜕t 2𝑚 𝜕𝑥2
This is the one dimensional time dependent schrodinger
equation.
• In three dimension, it takes the form,
𝜕𝛹 −ℏ2 𝜕2𝛹 + 𝜕2𝛹 + 𝜕2𝛹 + 𝑉𝛹
iℏ =
𝜕t 2𝑚 𝜕𝑥2 𝜕𝑦2 𝜕𝑧2

OR

𝜕𝛹 −ℏ2 2 + 𝑉𝛹
iℏ = 𝛻𝛹
𝜕t 2𝑚
Time independent schrodinger equations
• Again consider the solution of wave equation,
−𝑖
(𝐸𝑡−𝑝𝑥)
𝛹= 𝑎𝑒 ℏ

−𝑖𝐸𝑡 𝑖𝑝𝑥
It may be written as, 𝛹 = 𝑎𝑒 ℏ 𝑒
ℏ

−𝑖𝐸𝑡
𝛹 = 𝛹0𝑒 ℏ ----------(1)
differentiating 𝛹 partially wrt ‘t’,
−𝑖𝐸𝑡
𝜕𝛹 −𝑖𝐸
= 𝛹0 𝑒 ℏ ---------(2)
𝜕𝑡 ℏ
differentiating 𝛹 partially wrt ‘x’ twice,
𝜕2𝛹 𝜕2𝛹0 −𝑖𝐸𝑡
2 = 2 𝑒 ℏ ----------(3)
𝜕𝑥 𝜕𝑥
• Substituting (1), (2) and (3) in time dependent schrodinger equation,
𝜕𝛹 −ℏ2 𝜕2𝛹 + 𝑉𝛹
iℏ =
𝜕t 2𝑚 𝜕𝑥2

−𝑖𝐸𝑡
−𝑖𝐸 −ℏ2 𝜕2𝛹0 −𝑖𝐸𝑡 + 𝑉 −𝑖𝐸𝑡
iℏ𝛹0 𝑒 ℏ = 2 𝑒
ℏ 𝛹0𝑒 ℏ
ℏ 2𝑚 𝜕𝑥

−ℏ2 𝜕2𝛹0
𝐸𝛹0 = +vψ0
2𝑚 𝜕𝑥2

𝜕2𝛹0 2𝑚
+ (E-V)ψ0 = 0
𝜕𝑥2 ℏ2
This is schrodinger time independent equation in one dimension.
• In 3 dimension it can be written as,
2 2𝑚
𝛻 𝛹0+ 2 (E-V)ψ0 = 0
ℏ
 Application of schrodinger equation:
Particle in a box
• Electrons are restricted to move
around nucleus in a fixed orbits.
Behaviour of such bound electrons
can be described by particle in a
potential well.
• Consider a particle of mass ‘m’
confined in a one dimensional
potential box of infinite depth and finite m
length L, moving in x direction.
• The box has potential V=0 inside the
box and V=∞ outside the box, so that
particle cant leave the box.
• Potential energy V of the particle may be written as,
V=0 for 0<x<L
V=∞ for x≤0 and x≥L
• The particle cannot exist outside the box, so its wavefunction ψ is 0
for x≤0 and x≥L
• Within the box, Schrodinger equation becomes,
𝜕2𝛹 2𝑚𝐸
+ ψ= 0 ∵V=0(free particle)
𝜕𝑥2 ℏ2

𝜕2𝛹 2𝑚𝐸
2 +K2ψ = 0 where K=
𝜕𝑥 ℏ2

The general solution for this equation is

𝛹 = 𝐴𝑠𝑖𝑛𝐾𝑥 + 𝐵𝑐𝑜𝑠𝐾𝑥
Using the boundary conditions,

ψ = 0 at x =0 ψ = 0 at x = L
0 = A sin 0 + B cos 0 0 = A sin KL
0 = B cos 0 A ≠ 0 ⇒ sin KL = 0
cos 0 = 1 ⇒ B = 0 sin nπ = sin KL
nπ = KL
𝑛𝜋
K=
𝐿

𝑛𝜋x
Wave function 𝛹𝑛 (𝑥) = 𝐴 𝑠𝑖𝑛
𝐿
where n =1,2,3,4.....
• Equating expressions for K,
𝑛2𝜋2 2𝑚𝐸𝑛
2
=
𝐿 ℏ2
𝑛2𝜋2ℏ2
En =
2𝑚𝐿2
where n=1,2,3,4....
This is the energy eigen value for particle in a 1D box.
• So it is clear that inside an infinity deep potential well, particle
cannot have an arbitrary energy, but can have only certain discrete
energy corresponding to n=1,2,3...
• Permitted value of each energy level is called energy eigen value.
 𝑛2𝜋2ℏ2
• We have En =
2𝑚𝐿2
𝜋2ℏ2
• E1 =
2𝑚𝐿2

4𝜋2ℏ2
• E2 =
2𝑚𝐿2

9𝜋2ℏ2
• E3 =
2𝑚𝐿2

16𝜋2ℏ2
• E4 =
2𝑚𝐿2

Quantum numbers and enrgy levels of a particle

in a 1D box
• To find the normalized wavefunction,
+∞ ∗
‫׬‬−∞ 𝛹 𝛹𝑑𝜏 =1
𝐿
𝑛𝜋x 𝑛𝜋x
න 𝐴 𝑠𝑖𝑛 𝐴 𝑠𝑖𝑛 =1
0 𝐿 𝐿
𝐿
2 2
𝑛𝜋x
න 𝐴 𝑠𝑖𝑛 1 − 𝑐𝑜𝑠 2𝑥
0 𝐿 =1 sin2 x=
2
𝐴2 𝐿 2𝑛𝜋x
න 1 − 𝑐𝑜𝑠 𝑑𝑥 = 1
2 0 𝐿

𝐴2𝐿 2
=1⇒𝐴=
2 𝐿

2 n𝜋x
Then normalized wavefunction, 𝛹n (x) = sin
L L
• Probability distribution
2 n𝜋x
• We have, 𝛹n (x) = sin
L L
• Then probability distribution,
∗ 2 2 2 n𝜋x
│𝛹n 𝛹𝑛 │ (x) = sin
𝐿 L
• Maximum probability of
observing the particle is at the
mid point of the box for ground
state.
• In next higher state, the
maximum probabilities are at
one fourth and three fourth
distance from one end of the
box.
 In every quantum state there are
preferred positions of maximum
p r o b a b i l i t y. C l a s i c a l l y, t h e r e i s e q u a l
probability of finding the particle
anywhereinside the box.
• According to classical mechanics,
When a particle of energy E
approaches a potential barrier V, (E<V)
it bounces off without entering the
otherside.
• But in quantum mechanics, the
wavefunction representing the particle
doesnt vanish on the otherside.
• There is a fine probability of particle
penetrating through the barrier.
• This phenomenon of penetration
particles through barriers higher than
their energy is quantum tunneling.
• Find the least energy of an electron moving in one dimension in
an infinite high potential box of width 1Å.

𝑛2𝜋2ℏ2
We have En =
2𝑚𝐿2
𝜋2ℏ2
For least energy, n=1, E1 =
2𝑚𝐿2

mass of electorn = 9.1x10-31Kg

Answer=6.029x10-18J or 37.68eV
• Is it possible to observe the energy states of a ball of mass 10g
moving in a box along its length which is 10cm?

𝑛2𝜋2ℏ2
Energy states are given by, En =
2𝑚𝐿2
𝐸𝑛+1 (𝑛 + 1)2𝜋2ℏ2
=
2𝑚𝐿2
(2𝑛 + 1)𝜋2ℏ2
𝐸𝑛 + 1 − 𝐸𝑛 =
2𝑚𝐿2
substituting values, En + 1 − En= (2n+1)x3.426x10-45eV
• The gap between the two succesive levels is so small that we find a
continous distribution and hence energy states cant be observed.
• Calculate the ground state energy of an electron confined to a box
2Å wide.

m = 9.1x10-31Kg, L=2Å = 2x10-10m n=1

𝑛2𝜋2ℏ2
En =
2𝑚𝐿2
Answer = 1.507x-18J
• An electron is confined to a 1D box of side 1Å. Obtain first four
eigen values of energy in eV of the electron.

𝑛2𝜋2ℏ2
En =
2𝑚𝐿2
En=38n2 eV for L = 1Å

Answer: E1=38 eV
E2=152 eV
E3=342 eV
E4=608 eV