Welcome to

Engineering
Physics
(PHY1001)
Module - 2: Quantum Physics

Dr. Gounder Thangamani Jayaram

School of Advanced Sciences and
Languages (SASL)
Department of Physics
VIT BHOPAL University
Classical Mechanics:
The classical mechanics correctly explains the motion of celestial
bodies like planets, stars, macroscopic and microscopic terrestrial
bodies moving with non-relativistic speeds.

It treats particle nature and wave nature as quite distinct concepts.

 The phenomena associated with large size objects moving at speeds much below the
speed of light could be explained by classical mechanics(or also called as
Newtonian mechanics).
e.g., falling stones planetary motions etc.
 But the phenomena associated with small size objects moving at speeds of light
could be not be explained satisfactorily by classical mechanics
e.g., motions of electrons, atoms, molecules etc.

 It speaks energy to be emitted continuously.

 It predicts a precise trajectory with precisely specified

locations and momentum at each instant.
Dr. Gounder Thangamani Jayaram 2
FAILURES OF CLASSICAL MECHANICS:

1. The nature of emission of radiation from hot bodies.

Ex: black body radiation
2. Ejection of electrons from metal surface when radiation strikes it.
Ex: Photo electric effect
3. Variation of heat capacity of solids as a function of temperature.
4. Line spectra of atoms with special reference to hydrogen atoms.
5. It fails when applied to small particles such as electrons, atoms, molecules etc.
For example, according to classical mechanics, it should be possible to determine both
position and velocity (or momentum) of all moving particle but for microscopic particles
such as electrons, atoms, molecules etc, it was impossible.
6. The nature of bonding in molecules is not explained satisfactorily.

Failures of Classical mechanics led to the Need of Quantum mechanics.

Dr. Gounder Thangamani Jayaram 3
 Failures Of Classical Mechanics to explain
Black Body Radiation:
WHAT IS BLACK BODY….?
An object that absorbs ALL radiation falling on it, at all wavelengths, is called a blackbody.
 A black body is a object, which is capable of absorbing 100% of the radiation of all the
wavelengths that hits it. Therefore it reflects no radiation and appears perfectly black body.
 It is not only a perfect absorber but also a perfect radiator.
 When such a body is heated, it emits radiations which we call as blackbody radiations.
 A black body can radiate energy of all wavelengths when its heated to a suitable
temperature. This radiation is called Black Body Radiation.
 A cavity constructed with metallic hollow sphere of any material (iron or copper) with a tiny
hole and coated with lampblack on the interior portion resembles a perfectly blackbody. Any
light that strikes this hole enters the cavity, is reflected by the cavity wall, and is eventually
absorbed. When we heat the container at different temperatures, it emits radiations of all
frequencies (or wavelengths).
 The emitted radiation from a blackbody is a continuous spectrum.

Dr. Gounder Thangamani Jayaram 4

 Black body radiation
All bodies radiate energy in the form of photons. When these photons reach another surface, they
may either be absorbed, reflected or transmitted.
The behavior of a surface with incident radiation is described by the following quantities:

• Absorptivity (𝛼) is the fraction of the radiation absorbed upon the total incident radiation.

• Emissivity (𝜖) is the fraction of the total energy that radiated (emitted) from any body upon the
energy radiated (emitted) from the black body at the same temperature.

• Reflectivity (r) is the fraction of incident radiation reflected

• Transmissivity (𝜏) is the fraction of incident radiation transmitted.

Dr. Gounder Thangamani Jayaram 5

CHARACTERISTICS OF BLACK BODY RADIATION:

Black body radiation are characterised by Krichhoff‟s law, Stefan‟s law and Wein‟s law. According to
these laws, Black body radiation are stated as follows:

Krichhoff’s law :
The ratio of emissive power (𝒆𝛌 ) to the coefficient of absorption (𝒂𝛌 ) of a given wavelength is the
same for all the bodies at a given temperature and its equal to the emissive power (𝑬𝒃 ) of a
perfect black body at that temperature.
𝒆𝛌
= 𝑬𝒃
𝒂𝛌
 Stefan-Boltzmann Law:
The radiation energy (Q) emitted per unit time per unit area of a perfect black body is directly
proportional to the fourth power of its absolute temperature (T).

Q α 𝑻𝟒 OR Q = σ 𝑻𝟒

Where , Q is the total amount of radiation emitted by an object per square meter (Watts/𝑚2 )

σ is the proportionality constant known as Stefan-Boltzmann constant and its value is 5.67 ×
10−8 𝑊𝑎𝑡𝑡𝑠 𝑚−2 𝐾 −4 ; T - absolute temperature (k) 6
Dr. Gounder Thangamani Jayaram
CHARACTERISTICS OF BLACK BODY RADIATION:

 Wein’s law :
Wein‟s law states that the wavelength corresponding to maximum energy is inversely
proportional to absolute temperature (T).

𝒃
𝜆𝑚𝑎𝑥 =
𝑻

Where,
λmax is wavelength associated with maximum intensity,
T - Temperature, and
b = 2.897771955 × 10−3 mK (Wein‟s displacement constant).

Dr. Gounder Thangamani Jayaram 7

Energy Distribution in Black Body :
In 1895, at the University of Berlin, Wien and Lummer began to measure the radiation
coming out of blackbody.
The beam coming out of the hole was passed through a diffraction grating, which sent
the different wavelengths/frequencies in different directions, all towards a screen.
A detector was moved up and down along the screen to find how much radiant energy
was being emitted in each frequency range.
They found a radiation intensity/frequency curve close to the distributions in Figure 1.

By measuring the blackbody emission curves at different temperatures (Figure 1), they
were also able to construct two important phenomenological Laws (i.e., formulated
from experimental observations, not from basic principles of nature): Stefan-
Boltzmann‟s Law and Wien‟s Displacement Law.
Dr. Gounder Thangamani Jayaram 8
Energy Distribution in Black Body:
From the below graph, following observations are made:
1. The distribution of the energy is not uniform.
2. For a particular temperature, the intensity of radiation increases up to a particular
wavelength and then it is found to decrease with increase in wavelength.
3. As temperature increases, the peak energy shifts towards shorter wavelengths.
In 1893, Wein made the first attempt
to explain the observed results.
This holds good only for short
wavelengths and fails at higher
wavelengths and temperatures.
Conclusion: This holds good for short
wavelengths satisfactorily.

Later in 1900, the energy distribution

in the spectrum was explained by
Rayleigh and Jean.
Figure 1: Graphic representation of spectral distribution of blackbody radiation at different
temperatures. The Stefan- Boltzmann‟s Law is observed as the increase in the emission amplitude
with increasing temperature and the Wien‟s Displacement Law is observed as the shift to smaller
wavelength with increasing temperature. 9
Dr. Gounder Thangamani Jayaram
Rayleigh - Jeans law:
Lord Rayleigh and J. H. Jeans developed an equation which explained blackbody radiation at low
frequencies.
The Rayleigh-Jeans Law of radiation gives us the intensity of radiation released by a black body. The
law states that the intensity of the radiation emitted by a black body is directly proportional to the
temperature and inversely proportional to the wavelength raised to a power of four. However, this law
works for only low frequencies.
The Rayleigh-Jeans law approximates the spectral radiance of a black body as a function of its
wavelength at a given temperature. The Rayleigh-Jeans equation can be written as:
2𝑐𝑘𝐵 𝑇
𝐵𝛌 𝑇 = 4
𝛌

Where, 𝐵𝛌 = spectral radiance, c = speed of light, 𝑘𝐵 = Boltzmann constant, T= Temperature in

Kelvin. For frequency v, the Rayleigh‟s equation can be written as:

2𝝊2 𝑘𝐵 𝑇
𝐵𝜈 𝑇 = 𝑐2

The energy density 𝑢𝜈 per unit frequency interval at a frequency 𝝊 is, according to the Rayleigh-Jeans
equation for energy density ( 𝑢𝜈 ) can be written as:
8𝝿𝝊2 𝑘𝐵 𝑇
𝑢𝜈 =
𝑐2
Where, k is Boltzmann's constant, T is the absolute temperature of the radiating body, and c is the
speed of light in a vacuum.
Dr. Gounder Thangamani Jayaram 10
The experimental results showed a bell type of curve, but according to the Rayleigh-
Jeans law the frequency diverged as it neared the ultraviolet region.

Divergence of this equation for high frequencies (i.e., in the ultraviolet range) called the
ultraviolet catastrophe.

Figure 2: Energy density versus frequency according to Rayleigh-Jeans

Conclusion: Applicable at longer wavelength regions only.

Dr. Gounder Thangamani Jayaram 11
Example. 1:
The sun‟s surface temperature is 5700 K.
a. How much power is radiated by the sun?
b. Given that the distance to earth is about 200 sun radii, what is the maximum power
possible from a one square kilometer solar energy installation?
Solution:
(a) First, we calculate the area of the sun followed by the flux (power). The sun has a radius of
6.96 × 108 m.
The area of the sun is A = 4𝝿𝑹𝟐

The area of the sun is A=4𝝿𝑹𝟐

A = 4 (3.1416) (6.96 × 𝟏𝟎𝟖 m ) 𝟐
A = 6.08 × 𝟏𝟎𝟏𝟖 m𝟐

The power radiated from the sun (via Stefan-Boltzmann Law) is P = σ 𝑻𝟒

P = σ 𝑻𝟒
P = (𝟓. 𝟔𝟕 × 𝟏𝟎−𝟖 𝑾𝒂𝒕𝒕𝒔 𝒎−𝟐 𝑲−𝟒 ) (𝟓𝟕𝟎𝟎 𝑲)𝟒
P = 𝟓. 𝟗𝟖 × 𝟏𝟎𝟕 𝑾𝒂𝒕𝒕𝒔 /𝒎𝟐
12
This value is per square meter. Dr. Gounder Thangamani Jayaram
(b) To calculate the total power radiated by the sun is thus:
𝑷𝒕𝒐𝒕𝒂𝒍 = 𝑷𝑨

𝑷𝒕𝒐𝒕𝒂𝒍 = 𝑷𝑨

𝟐
= (𝟓. 𝟗𝟖 × 𝟏𝟎𝟕 𝑾𝒂𝒕𝒕𝒔 /𝒎𝟐 ) (6.08 × 𝟏𝟎𝟏𝟖 m )

= 3.6 × 𝟏𝟎𝟐𝟔 𝑾𝒂𝒕𝒕𝒔

Dr. Gounder Thangamani Jayaram 13

Example. 2:
If surface body temperature is 90 °F.
a. How much radiant energy in 𝑊 𝑚−2 would your body emit ?
b. What is the peak wavelength of emitted radiation ?
c. What is the total radiant energy emitted by your body in Watts ? Note: The average adult
human male has a body surface area of about 1.9 𝑚2 and the average body surface area
for a woman is about 1.6 𝑚2 .
Solution:
(a) 90 °F is 305 K. We use Stefan-Boltzmann Law . The total amount of radiation emitted will
be P = σ 𝑻𝟒
P = σ 𝑻𝟒
P = (𝟓. 𝟔𝟕 × 𝟏𝟎−𝟖 𝑾𝒂𝒕𝒕𝒔 𝒎−𝟐 𝑲−𝟒 ) (𝟑𝟎𝟓 𝑲)𝟒
P = 𝟒𝟗𝟏 𝑾𝒂𝒕𝒕𝒔 /𝒎𝟐
The peak wavelength of emitted radiation is found using Wien's Law:
𝒃
𝝀𝒎𝒂𝒙 = 𝑻

Where,
𝜆𝑚𝑎𝑥 is wavelength associated with maximum intensity,
T - Temperature, and b = 2.897771955 × 10−3 mK (Wein‟s displacement constant). 14
Dr. Gounder Thangamani Jayaram
 𝒃
𝜆𝑚𝑎𝑥 =
𝑻

2.898 × 10−3 m · K
=
𝑇

2.898 × 10−3 m · K
=
305 𝐾

= 9.5 × 10−6 m

= 9.5 μm

The total radiant energy density in Watts is :

Energymale = (491 𝑊𝑚−2 ) ( 1.9 𝑚2 )

= 933 W

Energyfemale = (491 𝑊𝑚−2 ) ( 1.6 𝑚2 )

= 786 W
15
Dr. Gounder Thangamani Jayaram
Example. 3:
If the Sun has a surface temperature of 5700 K, what is the wavelength of maximum intensity of
solar radiation?
Solution:
𝒃
If we substitute 5700 K for T in equation 𝜆𝑚𝑎𝑥 = 𝑻

Where, T is the absolute temperature in kelvin and b is a constant of proportionality called

Wien's displacement constant, equal to 2.89 × 10−3 m K, or more conveniently to obtain
wavelength in micrometers, b ≈ 2900 μm⋅K.

𝒃
𝜆𝑚𝑎𝑥 =
𝑻
𝟎.𝟎𝟎𝟐𝟗
= 𝟓𝟕𝟎𝟎

= 5.1 × 10−7 m.

16
Dr. Gounder Thangamani Jayaram
Example. 4:
a. At what wavelength does the sun emit most of its radiation if it has a temperature of 5,778 K?

Answer a
500 nm

b. At what wavelength does the earth emit most of its radiation if it has a temperature of 288 K?

Answer b
10.0 microns

Dr. Gounder Thangamani Jayaram 17

Planck’s law
The classical theory fails to explain the energy spectrum of a black body radiation.
According to the classical theory, an oscillating particle can have any value of frequency and emits
continuous energy.
Planck proposed the quantum theory in order to overcome the failure of the classical theory.
According to Planck‟s theory, matter is composed of a number of oscillatory particles.
These particles can vibrate at different frequencies.
The energy (E) of the oscillatory particles are quantised and it has the value.
E = nh𝜈
= n𝜀
where, E is the energy of the oscillator and ν is its frequency, n is a positive integer (n = 1,2,3,...),
and h is a proportionality constant know as Planck‟s constant and its value is 6.625 × 10−34 Joule
second.
According to the quantum theory, the particles in the matter vibrate, and hence, they cannot give out a
continuous radiation of energy.
On the other hand, the radiation is discontinuous, that is discrete, in bundles of packets known as
quanta or photon.
The vibrating particle in its quantised state cannot radiate energy and it can radiate energy only when
the oscillator moves from one state to another state. Therefore, the energy radiated by an oscillating
particle is E = nh𝜈
Thus, the present theory concludes that the exchange of energy between light and matter is only in
small packets or bundles or quanta of energy.
The photons can travel with the speed of light. 18
Dr. Gounder Thangamani Jayaram
Planck‟s Hypothesis and Radiation law
The following hypothesis are made by Planck‟s for the derivation of the radiation law:
1. Planck assumed that the black body is made up of a number of oscillating particles.
The particles can vibrate in all possible frequencies. The frequency of radiation from the black
body is the same as that of vibrating particles.
2. The oscillatory particles cannot emit energy continuously. They will radiate energy only in the
form of a discrete packet of energy, i.e., a small unit called as quanta or photon.
3. The vibrating particles can radiate energy when the oscillators move from one state to another
state. The radiation of energy is not continuous, but discrete in nature.

Consider a black body, it has „N‟ number of oscillators.

Let us consider the number of vibrating particles in the black body as 𝑁0 , 𝑁1 , 𝑁2 , 𝑁3, 𝑁4 , …. 𝑁𝑛 .
According to Planck‟s Hypothesis, the energy of the above particles can be written as 𝐸0 , 𝐸1 , 𝐸2 ,
𝐸3, 𝐸4 , …. 𝐸𝑛
Therefore, the total number of vibrating particles is:
𝑁 = 𝑁0 + 𝑁1 + 𝑁2 + 𝑁3 + 𝑁4 +…. + 𝑁𝑛 (Eq. 1)

Similarly, the total energy of body is:

E = 𝐸0 + 𝐸1 + 𝐸2 + 𝐸3 + 𝐸4 + ….+ 𝐸𝑛 (Eq. 2)
Therefore, the average energy of the particle
𝐸
𝜀 =𝑁 (Eq. 3)
Dr. Gounder Thangamani Jayaram 19
 20
Dr. Gounder Thangamani Jayaram
By using the power of power rule, the above equation can be written as

Therefore, this eq. can be written as

This is the total no. of oscillators in a blackbody

Polynomial expansion

Dr. Gounder Thangamani Jayaram 21

 Similarly, the total energy of all the oscillators in the blackbody can be written as :

This is the total energy of all the

oscillators in a blackbody

By substituting the total number of oscillatory particles and energy, respectively, from Eqs. (4)
and (5) in Eqs (3), we get :
𝐸
𝜀 =𝑁
𝜀= After rearranging we get
22
Dr. Gounder Thangamani Jayaram
 Number of oscillator
per unit volume in the
frequency range

Now multiplying with average energy of an oscillator

This above eq. is known as Planck’s eq. for radiation law.

Where, 𝜈 = c/𝛌
𝑐
‫׀‬d𝛌‫ ׀ = ׀‬−𝛌2 d𝛌‫׀‬
This above eq. is known as Planck’s radiation formula in term of frequency.

With the help of above equation of radiation law, Wein‟s

displacement law and Rayleigh Jeans law are modified.
Using the above results, the observed results in the energy
spectrum of black body radiations are explained successfully.
23
Dr. Gounder Thangamani Jayaram
Reduction of Planck’s law to Wien’s law and Rayleigh – Jeans law
Expanding 𝑒 𝑥 as power series we have

On substituting in Planck’s eq. for radiation law.

This eq. is the expression for Wien’s law of radiation. This eq. is the expression for Rayleigh – Jeans law of radiation.
Planck’s law reduces to Wien’s energy density distribution law in the shorter wavelength region, while24
Planck’s law reduces to Rayleigh – Jeans energy density distribution law in the longer wavelength region.
Dual Nature of Electromagnetic Radiation:
• Isaac Newton considered light to be a beam of particles.
• During the nineteenth century, some experiments concerning interference, diffraction, and polarisation of light
demonstrated the wave nature of light. But this wave nature of light could not be explain experimentally by the
photoelectric effect, compton effect etc.
• In 1887, Heinrich Rudolf Hertz discovered the photoelectric effect: electrons were observed to be ejected from metals
when irradiated with light. The photoelectric effect provides a direct confirmation for the energy quantization of light.
• The photoelectric effect is defined as the emission or ejection of electrons from the metal's surface in reaction to incident
light. The incident light's energy is absorbed by the metal's electrons, who then accumulate enough energy to be emitted
from the metal's surface. i.e. “knocked out”.
• Planck proposed that emission and absorption of energy does not take place continuously but at discrete intervals and in
discrete bundless or packets of energy. These packets of energy are known as quanta which we call as photons. The
energy of each photon is equal to h𝜈, where h is the Planck‟s constant and 𝜈 is the frequency of the associated radiation.
Hence, in general, light or any electromagnetic radiation has dual nature, meaning both wave nature and particle nature.
• Maxwell predicted that the energy of an electron that emitted is depends upon the intensity of the incident radiation.
• Lenard discovered that this was not the case. Rather, he discovered that the energies of an electron that emitted were
unaffected by the intensity of the incident radiation.
• In 1905, Einstein effectively answered this contradiction by arguing that incident light is made
up of discrete photons that interact with the electrons in the metal like distinct particles rather
than continuous waves.

Dr. Gounder Thangamani Jayaram 25

Photoelectric effect:
When light of certain frequency (visible or ultra violet radiation) strikes the surface of a metal,
electrons are ejected from the metal. This phenomenon is called as photoelectric effect.
The emitted electrons are called photoelectrons.
 When the tube is kept in the dark, the ammeter reads zero.
 When the light with different intensity strikes the surface of a emitter plate
(E), photoelectrons are ejected from the emitter plate (E).
 When a light with low intensity is used, there was no deflection in ammeter,
but when the light with high intensity is used, there was deflection in
ammeter, and the Current was produced.
 A light of smaller frequency cannot eject electrons no matter how long it
falls on the metal surface or how high is its intensity.
 For each metal, a certain minimum frequency of incident light is needed to
eject electrons. This is known as threshold frequency, ν0 . The threshold
frequency is different for different metals.
 The kinetic energy of ejected electrons is independent of the intensity of the
incident light but varies linearly with its frequency.
 The number of ejected electrons from the metal surface depends upon the
intensity of the incident light. The greater the intensity, the larger is the
number of ejected electrons.
 The kinetic energy of the emitted electrons increases linearly with increases
in frequency of incident light.
 This process is instantaneous, there is no time lag between incidence of light
and emission of electrons.
 The basic graph is plotted for intensity and current, from this kind of setup. 26
Dr. Gounder Thangamani Jayaram
 When we incident light on the plate, electrons emit and the current is increased even before the
voltage is applied.

 Now, we increase the voltage, we can observe that the current is also increased and become
saturated at one point.

 This saturation is because the electrons are emitted at the intensity of light.
 We have to bring back the current to 0. So, we can apply the reverse voltage, we can observe that
the current is reducing and becomes zero. It helps us to understand that the cathode plate is
observing the electrons emitted when we apply reverse voltage. ie., it stores back the potential.

27
Dr. Gounder Thangamani Jayaram
 When different frequency of light is used, we can observe that the stopping potential
is different for different frequency of light.
 Thus, the potential is based on the frequency not on the intensity.

Dr. Gounder Thangamani Jayaram 28

According to classical mechanics, energy of light depends on its intensity. If this
is true, then light of any frequency, if made sufficiently intense, can cause
ejection of electrons. But this does not happen.
 According to quantum mechanics, light consists of bundles of energy called photons, the
energy of each photon being equal to hν, where ν is frequency of light.
 When a photon of light strikes an electron in a metal, it imparts its entire energy ( = hν) to the
electron.
 This energy enables the electron to break away from the atom by overcoming the attractive
influence of the nucleus.
 Thus each photon can eject one electron. If the frequency of the light is less than threshold
frequency (ν0), there will no ejection of electron.
 When frequency of light falling on a metal surface is higher than the threshold frequency, then
some of its energy (which is equal to the energy to the energy binding the electron with the
nucleus) is consumed to separate the electron from the metal and the remaining energy will be
1
imparted to the ejected electron to give it certain velocity u (i.e., kinetic energy = 2 mu2 ).
 Energy of photon = Energy needed to liberate the electron + Maximum K.E of the liberated
electron
1
h𝜈 = 𝝓 + 2 𝑚𝑒 𝑢2 this is called as Einstein photoelectric equation …… (1)
1
where, 𝝓 is the threshold energy (or the work function W) of the metal, and 2 𝑚𝑒 𝑢2 is
the kinetic energy imparted for ejection of electron. where, 𝑚𝑒 is the rest mass of an electron.

 Evindently, 𝝓 = hν0 …………………. (2)

29
Dr. Gounder Thangamani Jayaram
Using eq. (2) into the eq. (1)
1
h𝜈 = hν0 + 𝑚 𝑢2
2 𝑒

1
h𝜈 − hν0 = 𝑚 𝑢2
2 𝑒
1
𝑚 𝑢2 = h (𝜈 − ν0 ) ………. (3)
2 𝑒

 The energies of photoelectrons can be measured by applying a negative voltage so that the
speed can be restored.

 The maximum negative potential required to stop completely the photoelectric current is
called the stopping potential.
𝑒𝑉𝑠 = h 𝜈 − 𝝓

Note:

1
 Note: kinetic energy = 2 mu2

30
Dr. Gounder Thangamani Jayaram
Applications of Photoelectric effect:

There are plenty of applications in day to day life.

31
Dr. Gounder Thangamani Jayaram
Example 1 : Calcium
a. What is the energy in joules and electron volts of a photon of 420-nm violet light?
b. What is the maximum kinetic energy of electrons ejected from calcium by 420-nm
violet light, given that the work-function for calcium metal is 2.71 eV?

Solution for (a)

Photon energy is given 6.63 × 10−34 𝐽. 𝑠 3.00 × 108 𝑚/𝑠
by: E=
420 × 10−9 𝑚
E = hν
hc
E=
λ E = 4.74 × 10−19 𝐽
Converting to eV, the energy of the photon is:

1 𝑒𝑉
E = 4.74 × 10−19 𝐽
1.6 ×10−19 𝐽
E = 2.96 eV 32
Dr. Gounder Thangamani Jayaram
Solution for (b)

KE = hν - 𝝓
= 2.96 eV – 2.71 eV
= 0.246 eV

Where, hν is the photon energy and 𝝓 is the work function (or binding
energy) of the electron to the particular material.

Dr. Gounder Thangamani Jayaram 33

Example 2 :
The work function (Φ) of some metals is listed below. The number of metals which
will show photoelectric effect when light of 300nm wavelength falls on the metal is:

Solution:
The energy of radiation must be equal to or greater than the work functions of metals to
show photoelectric effect.
We need to convert wavelength of radiation into energy expressed in eV units.

Now convert this value into eV.

We know that:

Dr. Gounder Thangamani Jayaram 34

Conclusion:
 Since the work functions of only Li, Na, K and Mg fall below
4.134 eV, only these metals can show photoelectric effect upon
exposure of radiation of 300nm wavelength.

 The number of metals that can show photoelectric effect = 4.

Dr. Gounder Thangamani Jayaram 35

Example 3 :
The energy required to remove an electron from sodium is 2.3 eV. Does
sodium show a photoelectric effect for orange light with 𝛌 = 6800 Å ?
Solution:

Dr. Gounder Thangamani Jayaram 36

Dr. Gounder Thangamani Jayaram 37
Example 4 :

Solution:

38
Dr. Gounder Thangamani Jayaram
Dr. Gounder Thangamani Jayaram 39
Example 5 :

Solution:

40
Dr. Gounder Thangamani Jayaram
Dr. Gounder Thangamani Jayaram 41
De Broglie hypothesis
 Newtonian mechanics fails to explain the different phenomena which take place
at microscopic or atomic scale.
 Quantum theory was able to explain the light or radiation behaves like a wave
as well as particle.
 The actual experimentally verified truth about electromagnetic radiation or light
is that it has both wave-like and particle-like properties in different
circumstances.
 Its wave-like properties are explained based on the phenomena like interference,
diffraction, polarization etc., while the particle-like properties are explained
based on the phenomena like photoelectric effect, compton effect, etc.
 Therefore, the light or radiation behaves like a wave as well as particle. Thus,
the wave-particle property of light or radiation is known as dual nature of light.
42
Dr. Gounder Thangamani Jayaram
 In 1924, Louis de-Broglie extended the wave-particle dualism of the light to the
material particles.
 According to de-Broglie thought that similar to the dual nature of light, material
particles must also possess the dual characteristic properties of particle and wave.
 This means that material particles such as electrons should also sometimes behave
as particle nature and sometimes behave like a wave nature. This is known as de
Broglie hypothesis.
 Therefore, the material particles like electron, proton, neutron, atom or molecules
will have an associated wave with them known as matter waves or pilot waves or
de Broglie waves.
 One can prove the wave nature of the particle through simple experiments namely
Davission-Germer and Thomsons experiments.
 In both the experiments, the electrons have been selected to prove the wave nature
mainly due to its well-known particle –like characteristic properties. 43
Dr. Gounder Thangamani Jayaram
De Broglie Waves [Matter Waves] and properties:

 According to Planck‟s quantum theory of radiation, the energy of a photon can be

written as:
Note: If photon is assumed to
E = hν have wave like character
Eq. (1)

Where, E is the energy, h is the Planck‟s constant, and ν is the frequency of the wave.
 On the other hand, If the photon is assumed to have particle like character, then
according to the mass-energy relationship proposed by Max Plane and Einstein. The
energy of a photon can be written as:

2 Note: If photon is assumed to

E = 𝑚𝑐 have particle like character Eq. (2)

Where, E is the energy, m is the mass of a photon, and c is the velocity of light.
From equations (1) and (2), we get :

2
hν = 𝑚𝑐
Dr. Gounder Thangamani Jayaram 44
 hν = 𝑚𝑐 2
Note: Since,
𝑐 2 𝑐
h = 𝑚𝑐 ν=
λ λ

ℎ
= 𝑚𝑐
λ

ℎ
λ=
𝑚𝑐
Where, λ is the Wavelength, h is the Planck‟s constant, m is the mass of a photon, and c is the
velocity of light.
Dr. Gounder Thangamani Jayaram 45
  Now if instead of a photon, we consider a material particle of mass (m) is moving
with a velocity (v), then the momentum (mv) of the particle. Therefore, the
wavelength of the wave associated with this moving material particle is given by:

ℎ
λ= Eq. (3)

𝑚v
This equation (3) is known as the de Broglie wavelength of matter waves.
 The de Broglie wavelength (λ) (for a material particle that has a certain mass) is
related to its momentum (p), through the Planck‟s constant (h).

ℎ Planck′ s constant (ℎ)

λ= =
𝑚v Momentum (p)
ℎ
λ= Eq. (4)
p
Where, p = mv stands for the momentum of the material particle.
46
Dr. Gounder Thangamani Jayaram
 This equation (4) gives the wavelength of the waves associated with photon. This
relation shows that the wave nature, wave length (λ) associated with the photon is
related to the particle nature, momentum (p).

1
λ ∝
Momentum (p)
 It means that the wavelength of a particle in motion is inversely proportional to its
momentum.

 This wavelength is called as de Broglie wavelength of material

particle.
 A moving particle is always associated with a wave, called as de
Broglie matter wave, whose wavelength depend upon the mass of
the particle and its velocity. 47
Dr. Gounder Thangamani Jayaram
De Broglie Wavelength in terms of kinetic energy (K.E):

 If a particle has kinetic energy (K.E), Then kinetic energy of the material particle
is given by:
1
K.E = mV 2
2 De Broglie Wavelength is given by :

2(K.E) = mV 2 ℎ
λ=
𝑚2 𝑉 2 p
2(K.E) =
𝑚
p2 ℎ
2(K.E) =
𝑚 λ=
2m(K.E)
2m(K.E) = p2 This is the de Broglie wavelength
for particle in terms of K.E.
p = 2m(K.E) 48
Dr. Gounder Thangamani Jayaram
De Broglie Wavelength associated with an accelerated
charged particle:
If a charged particle, say an electron is accelerated by a potential difference of volts
(V), then its kinetic energy (K.E) is given by:
The de Broglie wavelength of matter waves is given by:
K.E = eV ℎ
ℎ λ=
1
𝑚𝑉 2 = eV λ= 2eV
2
𝑚v 𝑚 ∙
𝑚
𝑚𝑉 2 = 2eV ℎ 𝑚
λ=
𝑚 2eV
2eV
𝑉2 =
𝑚 ℎ
λ=
𝑉=
2eV 2meV
𝑚 This is the De Broglie Wavelength associated
Dr. Gounder Thangamani Jayaram with an accelerated charged particle: 49
 De Broglie Wavelength for an accelerated Electron:

Suppose an electron accelerates through a potential difference of volt (v). The work
done by electric field on the electron appears as the gain in its kinetic energy. That is

De Broglie Wavelength is given by :

E = eV
1 2
ℎ
2
𝑚𝑉 = eV λ=
p
1
𝑚2 𝑉 2 = meV
2 ℎ
𝑚2 𝑉 2 = 2meV λ=
2meV
p2 = 2meV This is the de Broglie wavelength
for electron moving in a potential
p = 2meV difference of volt (V).
Dr. Gounder Thangamani Jayaram
50
 De Broglie Wavelength for a particle in
Thermal Equilibrium:
According to kinetic theory of gases, the average K.E of the material particle is given
by: 3 De Broglie Wavelength is given by :
K.E = 𝑘𝑇
2
ℎ
1 3 λ=
2
𝑚𝑉 =2
2
𝑘𝑇 p

𝑚𝑉 2 = 3𝑘𝑇 ℎ
λ=
3mkT
𝑚2 𝑉 2 = 3m𝑘𝑇 This is the de Broglie wavelength
for particle in gaseous state.
p2 = 3m𝑘𝑇 Where, k is the Boltzmann’s constant
(1.38 × 10−23 𝐽 𝑘)
p = 3m𝑘𝑇 T is the absolute temperature of the particle.
Dr. Gounder Thangamani Jayaram 51
Properties of matter waves:
1. Matter waves are generated only, if the materials particles are in motion.
2. The wavelength associated with matter waves decreases with increases in the mass
of the particles.

ℎ
i.e. λ=
2meV

3. The matter waves are not electromagnetic waves.

4. Matter waves can travel faster than the velocity of light.
5. The velocity of the matter waves depend on the velocity of the material particle.
6. The phase velocity of matter waves is inversely proportional to its wavelength.
7. The velocity of matter waves is not constant as that of electromagnetic radiation and
moves faster than the velocity of light.
Dr. Gounder Thangamani Jayaram 52
Heisenberg’s Uncertainty principle:
 Uncertainty principle, also called Heisenberg uncertainty principle statement was formulated
in 1927 by the German physicist Werner Heisenberg, that the position and the velocity of an
object both cannot be measured exactly, at the same time, even in theory. The very concepts of
exact position and exact velocity together, in fact, have no meaning in nature.

 The measurement of physical quantities like position, momentum, time, energy etc. can be
measured accurately in macroscopic systems (i.e. classical mechanics).

 The measurement of physical quantities for particles like electrons, protons, neutrons, photons
etc. can not be measured accurate in microscopic systems. If the measurement of one is certain
and that of other will be uncertain.

 According to Heisenberg uncertainty principle statement, the position and the momentum of a
particle in an atomic system cannot be determined simultaneously and accurately. If Δx is the
uncertainty associated with the position of a particle and Δp𝑥 the uncertainty associated with its
momentum, then the product of these uncertainties will always be equal or greater than h/4π.
That is

If Δx is small, ΔPx will be large and vice versa. That is if one quantity is measured accurately,
53 the
other quantity becomes less accurate. Dr. Gounder Thangamani Jayaram
 It is impossible to know both the exact position and exact momentum of an object at the same
time.
 Mathematically, this occurs because the smaller Δx becomes, the larger Δpx must become in
order to satisfy the inequality. However, the more accurately momentum is known the less
accurately position is known (Figure 1).

 The animation shows the relevant spreads in the uncertainty for position and momentum of
light/photons (light wave's corresponding photon particle). From the result of de Broglie, we
know that for a particle with known momentum, p will have a precise value for its de Broglie
wavelength can be determined (and hence a specific color of the light). 54
Dr. Gounder Thangamani Jayaram
 This relationship also applies to energy and time, in that one cannot measure the precise
energy of a system in a finite amount of time.

 Uncertainties in the products of “conjugate pairs” (momentum/position) and (energy/time)

were defined by Heisenberg as having a minimum value corresponding to Planck‟s constant
divided by 4π.
Applications of the Uncertainty Principle:
1. The size of an atom can be determined.
2. The non-existence of electron in the nucleus can be proved.
3. The binding energy of the hydrogen atom can be calculated.
4. Strength of the nuclear force can be estimated. 55
Dr. Gounder Thangamani Jayaram
 Wave function:
 There is always a quantity associated with any type of waves, which varies
periodically with space and time.

For an example:
1. For sound waves, where pressure varies as they propagate in a medium.
2. For water waves, the quantity that varies periodically is the height of the water
surface vary with space and time.
3. In light waves, the quantity that varies periodically is the electric and magnetic field
vary with space and time.
 Then question arises for matter waves. As the matter waves travel, what is the quantity
that vary with space and time….?
 To answer these questions,
 For de Broglie wave or matter waves associated with a moving particle, the
quantity that vary with space and time, is called as wave function. 56
Dr. Gounder Thangamani Jayaram
 The variable quantity characterizing de Broglie waves associated with a material particle,
is called as the wave function, and its denoted by the symbol “Ψ”.
 The value of the wave function associated with a moving body at the particular point x,
y, z in space at time t, is related to the finding of the body there at the time.
 In quantum mechanics we are concerned with this wave function (Ψ) of the body.
 The wave function (Ψ) associated with a moving particle is a complex quantity with
both real and imaginary parts, and therefore it cannot have a direct physical meaning. It
may be expressed in the form.
Ψ (x, y, z, t) = a + ib eq. (1)
Where, a and b are real function of the variables (x, y, z, t).
 One can obtain the complex conjugate of Ψ which is denoted by Ψ* by changing i to - i,
Ψ* (x, y, z, t) = a - ib eq. (2)
Multiplying eq.(1) by eq. (2), one obtains
Ψ (x, y, z, t) Ψ* (x, y, z, t) = (a + ib)(a - ib)
Ψ (x, y, z, t) Ψ* (x, y, z, t) = 𝑎2 + 𝑏 2 eq. (3) 57
Dr. Gounder Thangamani Jayaram
The positive square root of Ψ (x, y, z, t) Ψ* (x, y, z, t) is represented as Ψ (x, y, z, t) , called as
the modulus of Ψ.
2
The quantity Ψ (x, y, z, t) is called the probability density (i.e. the product of Ψ Ψ* is
denoted by P).
However, the product of a complex number with its complex conjugate is a real and non-
negative number. Hence, this interpretation is possible.
P = Ψ (x, y, z, t) Ψ* (x, y, z, t)
2
= Ψ (x, y, z, t)
Ψ (x, y, z, t) 2 = 𝑎2 + 𝑏2 eq. (4)
Here, 𝑎2 + 𝑏 2 is a real quantity.
Maxborn has used the result (4) and interpreted as follows: For the motion of a particle, the
quantity is given by
2
PdV = Ψ (x, y, z, t) Ψ* (x, y, z, t)dV PdV = Ψ (x, y, z, t) dV
P = Ψ (x, y, z, t) 2 [Note: Where, dV is the volume element.] eq. (5)
Thus, P is the probability that the particle will be found in a volume element dV surrounding
58
the point at position (x,y,z) at time t. Dr. Gounder Thangamani Jayaram
Physical significance of wave function:
The wave function Ψ (x) and the probability distribution Ψ (x) 2 between a region M
and N for one dimensional wave function in graphical representation is as shown in
Fig.1.

Fig.1. wave function Ψ (x) and the probability distribution Ψ (x) 2

 Negative amplitude cannot give the probability of a wave function Ψ (x).

 It is thus clear that wave function Ψ (x) itself has no direct physical meaning.
59
Dr. Gounder Thangamani Jayaram
  The value of wave function Ψ (x) defining a moving particle in space at a certain
time is related to the finding of the particle in that region at that time.
 But a wave function Ψ (x) has both positive and negative amplitude, and if wave
function Ψ (x) is to give the probability, then negative probability is meaning less.
 Hence, the probability is defined in terms of the probability distribution Ψ (x) 2

which is always real and positive quantity.

 Secondly, the particle to be defined by probability distribution Ψ (x) 2 either exists

or does not exist that is the total probability, i.e., either zero or unity.

∞ 2
If P= −∞
Ψ (x ) dx = 0 Then particle does not exist.

and
∞ 2
If P= −∞
Ψ (x ) dx = 1 Then particle exists somewhere in space at all time.

Dr. Gounder Thangamani Jayaram 60

 For the motion of a particle in one dimension space, is given by
Pdx = Ψ (x, t)
= Ψ (x, t) 2 dx eq. (6)

 In this case is Ψ (x, t) 2 is called the probability per unit distance.

 Thus the total probability is
∞ 2
𝑃X = −∞
Ψ (x, t) dx eq. (7)
 For the one dimensional space along the X-axis.
 The normalising condition for the wave function for the motion of particle in one
∞ 2
dimension is given by 𝑃X = −∞
Ψ (x, t) dx
∞
𝑃X = −∞
Ψ∗(x, t) Ψ (x, t) dx = 1 eq. (8)
 When equation (8) is true, wave function is said to be normalised. A wave
function which satisfies the condition of equation (8) is said to be normalised (to
unity).
 This is called the normalization condition of the wave function.
61
Dr. Gounder Thangamani Jayaram
 For the motion of a particle in three dimensional space, is given by
∞ 2
𝑃X = −∞
Ψ (x, y, z, t) dv eq. (9)

 The above integrals must be finite in order to represent a real particle.

 The normalising condition for the wave function for the motion of a particle in three
dimension is ∞ 2
𝑃X = −∞
Ψ (x, y, z, t) dv = 1 eq. (10)
Where, Ψ is a wave function of the space co-ordinates (x, y, z).
 This is called the normalization condition of the wave function.

 If a wave function does not satisfy the normalisation condition of equation (10),
then it must be multiplied by a constant factor, called as the normalisation factor.
For example,
Ψ2 dx = N (Note: N ≠ 1) eq. (11)
1 1
 The normalisation factor will be and the normalised wave function will be Ψ.
𝑁 𝑁

1
 One can easily see that Ψ will be as good as wave function Ψ itself.
𝑁 62
Dr. Gounder Thangamani Jayaram
Schrodinger Wave Equation:
 In 1962, Schrodinger developed mathematical equations to explain both
microscopic and macroscopic particles by predicting the wave function at any
particular point.
 Schrodinger equation is one of the basic equations in quantum mechanics like
Newton‟s law of motion.
 Schrodinger derived two forms of wave equation, namely time independent wave
equation and time dependent wave equation to explain the dual nature of matter
waves.
 As de Broglie made two assumption to derive the equation for the matter wave.
 In his first assumption, the de Broglie wavelength concept was applied to any
matter waves under any field of force.
 When such an external force is applied, the particles will have both potential
63
energy (P.E) and Kinetic energy (K.E), i.e., Dr. Gounder Thangamani Jayaram
 E = P.E + K.E
1
E = V + mv 2
2

p2
E = V +
2𝑚
Rearranging the Eq., we get

p = 𝟐𝒎 (𝑬 − 𝑽)
According to de Broglie wavelength, we know that,

ℎ
λ=
p
ℎ
The de Broglie wavelength λ=
𝟐𝒎 (𝑬 − 𝑽)
64
Dr. Gounder Thangamani Jayaram
 According to the de Broglie second assumption, the one dimensional wave function
associated with the particle is given as

Ψ = Ψ𝑜 𝑒 −𝑖 ω 𝑡
Where, Ψ𝑜 is the amplitude of the wave function at the point (x, y, z), and

ω is the angular velocity of the particle wave.

We know that, 𝝎 = 2πν

Where, ν is the frequency of radiation.

Dr. Gounder Thangamani Jayaram 65

Schrodinger time independent wave equation:
 Consider a particle of mass (m) is moving with a velocity (v).
 Let Ψ be the wave function of the particle along the x, y, and z co-ordinate axes at
any time. i.e., Ψ (x, y, z, t).
 Then, the de Broglie wavelength associated with the wave function 𝚿 (x, y, z, t) at
any given instant of time (t) is given by :
ℎ
λ=
mv
 Based on the Cartesian co-ordinates one can write the classical differential wave
equation for the motion of particle in waves, moving with a wave velocity (u) can
be written as:
Eq. (1)

66
Where, u is the wave velocity of particle waves.
 The solution of differential equation (1) gives 𝚿 (x, y, z, t) as a periodic
displacement in terms of time as below:

𝚿 (x, y, z, t) = 𝚿𝒐 (x, y, z) 𝒆−𝒊 𝝎 𝒕 Eq. (2)

Where, Ψ𝑜 is the amplitude of the wave function at the point (x, y, z) considered and

ω is the angular velocity of the particle wave.

𝛛𝟐 𝚿
 The value of can be obtained by differentiating equation (2) twice w.r.t time
𝛛𝐭 𝟐
(t), then we get

𝛛𝚿
= 𝚿𝒐 𝒆−𝒊 𝝎 𝒕 × (−𝒊 𝝎 )
𝛛𝐭

𝛛𝚿 𝑵𝒐𝒕𝒆: 𝚿 = 𝚿𝒐 𝒆−𝒊 𝝎 𝒕
= −𝒊 𝝎 𝚿
𝛛𝐭 Dr. Gounder Thangamani Jayaram 67
 Again differentiating w.r.t time (t), we get

𝛛𝟐 𝚿
= ( − 𝒊 𝝎 ) 𝚿𝒐 𝒆−𝒊 𝝎 𝒕 × (−𝒊 𝝎 )
𝛛𝐭 𝟐

𝛛𝟐 𝚿
= 𝒊𝟐 𝝎𝟐 𝚿𝒐 𝒆−𝒊 𝝎 𝒕
𝛛𝐭 𝟐

𝛛𝟐 𝚿
= 𝒊𝟐 𝝎𝟐 𝚿 𝑵𝒐𝒕𝒆: 𝒊𝟐 = - 1
𝛛𝐭 𝟐

𝛛𝟐 𝚿
= - 𝝎𝟐 𝚿 Eq. (3)
𝛛𝐭 𝟐
 Substituting equation (3) in equation (1)

68
Dr. Gounder Thangamani Jayaram
𝛛𝟐 𝚿 𝛛𝟐 𝚿 𝛛𝟐 𝚿 𝟏
+ + = × - 𝝎𝟐 𝚿
𝛛𝐱 𝟐 𝛛𝐲 𝟐 𝛛𝒛𝟐 𝒖𝟐

𝛛𝟐 𝚿 𝛛𝟐 𝚿 𝛛𝟐 𝚿 − 𝝎𝟐 𝚿 We know that, 𝝎 = 2πν

+ + =
𝛛𝐱 𝟐 𝛛𝐲 𝟐 𝛛𝒛𝟐 𝒖𝟐 Where, ν is the frequency of radiation.

𝛛𝟐 𝚿 𝛛𝟐 𝚿 𝛛𝟐 𝚿 − (𝟐𝝅𝝂)𝟐 𝚿
+ + =
𝛛𝐱 𝟐 𝛛𝐲 𝟐 𝛛𝒛𝟐 𝒖𝟐

𝛛𝟐 𝚿 𝛛𝟐 𝚿 𝛛𝟐 𝚿 − 𝟒 𝝅𝟐 ν𝟐 𝚿
+ + = ν =u/λ
𝛛𝐱 𝟐 𝛛𝐲 𝟐 𝛛𝒛𝟐 𝒖𝟐
𝛛𝟐 𝚿 𝛛𝟐 𝚿 𝛛𝟐 𝚿 − 𝟒 𝝅𝟐 ν𝟐 𝚿
+ + =
𝛛𝐱 𝟐 𝛛𝐲 𝟐 𝛛𝒛𝟐 (νλ)𝟐

𝛛𝟐 𝚿 𝛛𝟐 𝚿 𝛛𝟐 𝚿 − 𝟒 𝝅𝟐 ν𝟐 𝚿
+ + =
𝛛𝐱 𝟐 𝛛𝐲 𝟐 𝛛𝒛𝟐 ν𝟐 λ𝟐 69
 𝛛𝟐 𝚿 𝛛𝟐 𝚿 𝛛𝟐 𝚿 − 𝟒 𝝅𝟐 𝚿
+ + = Eq. (4)
𝛛𝐱 𝟐 𝛛𝐲 𝟐 𝛛𝒛𝟐 λ𝟐

 According to the de Broglie wavelength, we know that

ℎ
λ= Eq. (5)
p

 According to the de Broglie’s first assumption, the de Broglie wavelength concept

was applied to any matter waves under any field of force. When such an external
force is applied, the particles will have both potential and kinetic energy. So the total
energy of the particle is given by:
E = P.E + K.E 70
Dr. Gounder Thangamani Jayaram
 E = P.E + K.E
1
E = V + mv 2
2

1
E - V= mv 2
2
Multiplying m on both the side, we get
1 2 2
m(E - V) = m v
2
Rearranging the Eq., we get

2m(E - V) = m2 v 2

2m(E - V) = 𝑝2

p = 𝟐𝒎 (𝑬 − 𝑽) 71
Dr. Gounder Thangamani Jayaram
 Substituting the value of p in λ
ℎ
λ=
p

Then the de Broglie wavelength becomes

ℎ
λ= Eq. (6)
𝟐𝒎 (𝑬 − 𝑽)

ℎ 2
λ2 = Eq. (7)

𝟐𝒎 (𝑬 − 𝑽) 72
Dr. Gounder Thangamani Jayaram
 Substituting equation (7) in equation (4)

𝛛𝟐 𝚿 𝛛𝟐 𝚿 𝛛𝟐 𝚿 − 𝟒 𝝅𝟐 𝚿
+ + = Eq. (4)
𝛛𝐱 𝟐 𝛛𝐲 𝟐 𝛛𝒛𝟐 λ𝟐

𝛛𝟐 𝚿 𝛛𝟐 𝚿 𝛛𝟐 𝚿 − 𝟒 𝝅𝟐 𝚿
+ + = ℎ2
𝛛𝐱 𝟐 𝛛𝐲 𝟐 𝛛𝒛𝟐
𝟐𝒎 (𝑬 − 𝑽)

𝛛𝟐 𝚿 𝛛𝟐 𝚿 𝛛𝟐 𝚿 − 𝟒 𝝅𝟐 𝚿
+ + = × 𝟐𝒎 (𝑬 − 𝑽)
𝛛𝐱 𝟐 𝛛𝐲 𝟐 𝛛𝒛𝟐 𝒉𝟐

𝛛𝟐 𝚿 𝛛𝟐 𝚿 𝛛𝟐 𝚿 − 𝟖 𝝅𝟐 𝒎 (𝑬 − 𝑽)𝚿
+ + =
𝛛𝐱 𝟐 𝛛𝐲 𝟐 𝛛𝒛𝟐 𝒉𝟐
Dr. Gounder Thangamani Jayaram 73
  We know that 𝛻 2 is the Laplacian operator and is equal to

𝛛𝟐 𝛛𝟐 𝛛𝟐
𝛻2 = + +
𝛛𝐱 𝟐 𝛛𝐲 𝟐 𝛛𝐳 𝟐

 Laplacian operator is an operator, operates on the wave function and reproduces

the corresponding wave function and it energy.

2 8 π2 m (E − V)Ψ
𝛻 Ψ = −
h2

8 π2 m (E − V)Ψ
𝛻2 Ψ + =0 Eq. (8)
h2
This equation is known as Schrodinger’s time independent wave equation.

 Let us now introduce ħ in equation (8) 74

Dr. Gounder Thangamani Jayaram
 ℎ
ħ =
2π
2π ħ = ℎ
ℎ = 2π ħ
ℎ2 = 4 π2 ħ2
Where, ħ is called as standardized Planck‟s constant or Factored Planck‟s constant.

 Therefore equation (8) is modified by substituting ħ

2 8 π2 m (E − V)Ψ
𝛻 Ψ+ =0 Eq. (8)
h2

8 π2 m (E − V)Ψ
𝛻2 Ψ + =0
4π 2 ħ2
Dr. Gounder Thangamani Jayaram
75
 2 2m (E − V)Ψ
𝛻 Ψ+ =0
ħ2

 In some special case:

 For a free particle V = 0 (i.e., P.E is Zero) therefore Schrodinger wave equation
becomes :

2 2m E Ψ
𝛻 Ψ+ =0
ħ2

 Since for a free particle, the potential energy V = 0 , one cannot use the
Schrodinger time independent equation.
 Hence, a more general time dependent Schrodinger equation is required.

Dr. Gounder Thangamani Jayaram 76

Schrodinger’s time dependent wave equation:

 Schrodinger time dependent wave equation is obtained from

Schrodinger time independent wave equation.
 The classical differential equation for wave motion is given by:

Eq. (1)

Where, u is the wave velocity of particle waves.

 Equation (1) can be written as

𝟏 𝛛𝟐 𝚿
𝛻2 Ψ = × Eq. (2)
𝒖𝟐 𝛛𝒕𝟐
Dr. Gounder Thangamani Jayaram 77
  We know that 𝛻 2 is the Laplacian operator and is equal to

𝛛𝟐 𝛛𝟐 𝛛𝟐
𝛻2 = + +
𝛛𝐱 𝟐 𝛛𝐲 𝟐 𝛛𝐳 𝟐

 Laplacian operator is an operator, operates on the wave function and reproduces

the corresponding wave function and it energy.

 The solution of differential equation (2) gives 𝚿 (x, y, z, t) as a periodic

displacement in terms of time as below:

𝚿 (x, y, z, t) = 𝚿𝒐 (x, y, z) 𝒆−𝒊 𝝎 𝒕

𝚿 = 𝚿𝒐 𝒆−𝒊 𝝎 𝒕 Eq. (3)

Where, Ψ𝑜 is the amplitude of the wave function at the point (x, y, z) considered and
78
ω is the angular velocity of the particle wave.
 Differentiating equation (3) w.r.t time (t), then we get

𝛛𝚿
= 𝚿𝒐 𝒆−𝒊 𝝎 𝒕 × (−𝒊 𝝎 )
𝛛𝐭

𝛛𝚿
= −𝒊 𝝎 𝚿𝒐 𝒆−𝒊 𝝎 𝒕
𝛛𝐭

𝛛𝚿
= −𝒊 𝝎 𝚿 𝑵𝒐𝒕𝒆: 𝚿 = 𝚿𝒐 𝒆−𝒊 𝝎 𝒕
𝛛𝐭

𝛛𝚿
= −𝒊 (𝟐𝝅𝝂 ) 𝚿 Eq. (4) 𝑵𝒐𝒕𝒆: Since 𝝎 = 2πν
𝛛𝐭

𝛛𝚿 𝑬
= −𝒊 (𝟐𝝅 )𝚿 𝑵𝒐𝒕𝒆: Since E = h ν
𝛛𝐭 𝒉
𝑬
ν=
𝒉
Dr. Gounder Thangamani Jayaram 79
 𝛛𝚿 𝑬
= −𝒊 (𝟐𝝅 )𝚿
𝛛𝐭 𝒉

𝛛𝚿 𝑬 𝑵𝒐𝒕𝒆: Since ℎ = 2π ħ
= −𝒊 (𝟐𝝅 ) 𝚿
𝛛𝐭 2π ħ

𝛛𝚿 𝑬
= −𝒊 𝚿 Eq. (5)
𝛛𝐭 ħ
Multiplying 𝒊 on both the side in equation (5), we get

𝛛𝚿 𝟐 𝑬
𝒊 =−𝒊 𝚿
𝛛𝐭 ħ

𝛛𝚿 𝑬
𝒊 = 𝚿 𝑵𝒐𝒕𝒆: Since 𝒊𝟐 = - 1
𝛛𝐭 ħ Dr. Gounder Thangamani Jayaram 80
 𝜕Ψ
𝑖ħ =𝐸𝛹
𝜕t

𝜕Ψ
𝐸𝛹= 𝑖ħ Eq. (6)
𝜕t
 According to Schrodinger’s time independent wave equation:

2 2m (E − V)Ψ
𝛻 Ψ+ =0
ħ2

2 2m E Ψ 2𝑚 V 𝛹
𝛻 Ψ+ - =0
ħ2 ħ2

Substituting the value of 𝐸𝛹 , we get

2 2m 𝜕𝛹 2𝑚 V 𝛹
𝛻 Ψ+ × 𝑖ħ - =0
ħ2 𝜕𝑡 ħ2
81
Dr. Gounder Thangamani Jayaram
 ħ2
Multiplying by , we get
2m
ħ2 2m ħ2 𝜕𝛹 2𝑚 V 𝛹 ħ2
2m
× 𝛻2 Ψ+
ħ2
×
2m
× 𝑖ħ
𝜕𝑡
-
ħ2
×
2m
=0

ħ2 𝜕𝛹
2m
× 𝛻2 Ψ+ 𝑖ħ
𝜕𝑡
- V𝛹 =0

ħ2 𝜕𝛹
2m
× 𝛻2 Ψ - V𝛹 =- 𝑖ħ
𝜕𝑡

ħ2 𝜕𝛹
−
2m
× 𝛻2 Ψ + V𝛹 = 𝑖ħ
𝜕𝑡
Dr. Gounder Thangamani Jayaram 82
 ħ2 2 𝜕𝛹
− ×𝛻 + V 𝛹= 𝑖ħ Eq. (7)
2m 𝜕𝑡
 This is known as Schrodinger wave equation containing the time.

 H is the Hamiltonian operator and is equal to

ħ2
H=− × 𝛻2 + 𝑉
2𝑚
 Substituting the value of H in equation (7), we get
𝜕𝛹
H𝛹 = 𝑖ħ
𝜕𝑡

H𝛹 = E𝛹 Eq. (8)

 This is known as Hamiltonian form of the Schrodinger wave equation.

83
Dr. Gounder Thangamani Jayaram
 H𝛹 = E𝛹
𝜕Ψ 𝜕
 Where, 𝐸 𝛹 = 𝑖ħ is an energy operator, while operator 𝑖ħ 𝜕t,
𝜕t

operates on Ψ, gives Energy (E).

 Schrodinger time dependent wave equation can be either in the

form of equation (7) or (8) depending on the application.

Dr. Gounder Thangamani Jayaram 84

Application of Schrodinger’s wave equation:
Particle in a 1 D box
(Electron in an infinitely deep potential well or particle in an infinite well)

 Let us consider a particle of mass (m) and

energy (E) is travelling along the X-direction
inside a box of width x = 0 to x = L.
 Its motion is restricted by rigid walls of infinite
height at x = 0 and x = L as shown in Fig.1.
 The particle does not lose any energy when it
collides with the walls and hence the total
energy (E) of the particle remains constant.
 The total energy of the particle cannot be
infinite, since it is restricted to move within the Fig.1. Particle in a 1 D box
Dr. Gounder Thangamani Jayaram 85
box.
 Thus, the potential energy (V) of the particle is considered to be zero inside
the box and infinite outside the box.
V (x) = 0 when 0 < x < L

V(x) = ∞ when x ≤ 0 and x ≥ L

 When the potential energy (V = 0), then particle moves in a force free
region and the time independent Schrodinger wave equation for a free
particle (i.e. V = 0) moving in one dimension is given by :

 According to Schrodinger’s time independent wave equation:

2 2m (E − V)Ψ
𝛻 Ψ+ =0
ħ2

𝜕2 Ψ 2m E Ψ 2𝑚 V 𝛹
𝜕𝑥 2
+ - =0 Eq. (1)
ħ2 ħ2 86
Dr. Gounder Thangamani Jayaram
 Since, V = 0 for the free particle between the walls, the Eq. (1) reduces to:

𝜕2 Ψ 2m E Ψ
𝜕𝑥 2
+ =0 Eq. (2)
ħ2

𝜕2 Ψ
𝜕𝑥 2
+ k2Ψ = 0 Eq. (3)

Where, k is called as wave vector and the value of k is given by:

2mE 2 2mE
k= or k =
ħ2 ħ2

 The general solution of this differential Eq. (3) is given by:

Ψ(x) = A sin kx + B cos kx Eq. (4)

 Where, A and B is the amplitude of the wave function.

 Here, A and B are two unknown constants. The values of the constants A and B are
determined by applying the boundary conditions. 87
Dr. Gounder Thangamani Jayaram
 Applying the first boundary condition that Ψ = 0 at x = 0 to Eq. (4)

Ψ(x) = A sin kx + B cos kx Eq. (4)

Ψ(0) = A sin (0) + B cos (0) Note: when, x = 0 ; Ψ = 0

0 = A× 0 + B × 1 Note: sin (0) = 0 ; cos (0) = 1

0=B B=0
 Substitute the value of “B” in Eq. (4), we get

Ψ(x) = A sin kx + B cos kx

Ψ(x) = A sin kx Eq. (5)

88
Dr. Gounder Thangamani Jayaram
 Applying the second boundary condition that Ψ = 0 at x = L to Eq. (5)
Ψ(x) = A sin kx
0 = A sin kL
A sin kL = 0 Eq. (6)

 It is found that either A = 0 or sin kL = 0 ; A cannot be zero since already one of

the constant B = 0.
 Here, if A is also zero, then the wave function 𝚿(x) is zero even in between the
walls of the box. Hence, A cannot be zero.
 We know that the particle is present inside the box and hence A ≠ 0. Therefore, we
can write, sin kL = 0.
 But sin kL = 0, only when kL takes the values of nπ. (i.e., sin kL = sin nπ)
nπ
i.e., kL = nπ k = Eq. (7)
𝑳
89
Where, n is positive integer 1, 2, 3, …… and because sin π, sin 2π, sin 3π…. All are zero
 On squaring Eq. (7), we have
2 2
2
n π
k = Eq. (8)
L2
 Substituting the value of k 2 in Eq. (8), we get

2mE n2 π 2 2mE
2
= Note : k 2 =
ħ2
ħ L2
Rearranging the above equation, we get

n 2 π2 ħ2 Note : ħ =
ℎ
E = × 2π
L2 2m
ℎ
Substituting the value of ħ ( = ) , we get
2𝜋

n2 π2 1 ℎ2
E = × ∙ 2
L2 2m 4𝜋 90
 n 2 π2 h2 n2 ℎ 2
E = × E =
L2 8mπ2 8mL2
Where, n is positive integer 1, 2, 3, ……

 Thus, it can be concluded from the above equation that inside an

infinite potential well, the particle cannot have an arbitrary energy,
but can have only certain discrete energy value corresponding to n.
 Each permitted energy is called the Eigen values of the particle in
the well and constitutes the energy levels of the system.
n2 h2
En = Eq. (9)
8mL2 Where, n is positive integer 1, 2, 3, ……

 This Eq. (9) is known as the Energy Eigen values of a free

particle in one dimensional box. 91
Dr. Gounder Thangamani Jayaram
 Each value of En is known as Eigen value of the particle in the
1D box and constitute the energy level of the system as shown in
Fig.2.
 The integer “n” corresponding to the energy level En is called
“Quantum number”.
 Case (1): when n = 0
 Here, n = 0 is excluded because then E0 = 0, which is not true
quantum mechanically.
 For n = 0 the wave function Ψ becomes zero, which is not
physically permissible.
 Because the particle is not at rest even at 0 k temperature.
Dr. Gounder Thangamani Jayaram 92
 Case (2): when n = 1 n2 h 2
En =
8mL2
 When the particle has minimum energy, this minimum energy is
called as zero point energy.

h2
n=1 E1 =
8mL2

 Case (3): when n = 2

4h2
n=2 E2 = 4E1
8mL2

 Case (4): when n = 3

9h2
n=3 E3 = 9E1
8mL2 93
Dr. Gounder Thangamani Jayaram
 Case (5): when n = 4
16h2
n=4 E4 = 16E1
8mL2
and so on…..
 The discrete energy spectrum of the particle inside the box is shown in Fig.2.

 Thus, the particle will have

energy values given by Eq. (9).
 Its energy is quantised.
 However, if the particle is
outside the box, it is a free
particle and will have
continuous energy spectrum.
Fig.2. discrete energy spectrum. 94
Dr. Gounder Thangamani Jayaram
Eigen functions:
 The wave functions Ψ corresponding to each Eigen value are
called Eigen functions.
 The wave function of a particle in a box with energy En is given
by:
𝑛π x
Ψn (x) = A sin 𝐿
Eq. (1)

 Let us find the value of “A” by applying the normalization

condition.
∞
Ψn 2 𝑑𝑥 = 1
−∞
Dr. Gounder Thangamani Jayaram 95
 Since the particle is somewhere inside the box. Thus, the
probability of finding the particle inside the box of length is given
by:
𝐿
2 Note: since the particle
Ψn 𝑑𝑥 = 1 is confined within
0 x = 0 to x = L.

𝐿
𝑛π x 2
A sin 𝑑𝑥 = 1
0 𝐿

𝐿
2 2
𝑛π x
A sin 𝑑𝑥 = 1
0 𝐿
Dr. Gounder Thangamani Jayaram 96
 Note:
𝐿
2 2 𝑛π x 1 −cos2θ
A sin 𝑑𝑥 = 1 sin 2 θ =
2
0 𝐿

𝑛π x
𝐿 1 − cos2
A2 𝐿 𝑑𝑥 = 1
0 2

2 𝐿
A 𝑛π x
1 − cos2 𝑑𝑥 = 1
2 0 𝐿

𝐿 𝐿
A2 𝑛π x
𝑑𝑥 − cos2 𝑑𝑥 = 1
2 0 0 𝐿
Dr. Gounder Thangamani Jayaram 97
 A2 𝐿 𝐿
𝑛π x
𝑑𝑥 − cos2 𝑑𝑥 = 1
2 0 0 𝐿
2 𝐿
A 𝐿
𝐿 𝑛π x
𝑋 0 − sin2 =1
2 2𝑛π 𝐿 0
The second term of the integral becomes zero at both the limits
2 2
A 𝐿 A 𝐿 2
𝑋 0 =1 =1 𝐴=
2 2 𝐿
Here, A is the normalisation constant.
Substituting the value of “A” in Eq. (1).

2 𝑛π x
Ψn = 𝐿
sin
𝐿
Where, n is positive integer 1, 2, 3, …… Eq. (2)

98
This Eq. (2) is known as the normalised Eigen functions of the particle in 1D box.
 Although Ψn may be negative as well as positive, Ψn 2 is
always positive and since Ψn is normalised, its value of Ψn 2 at a
given x is equal to the probability density (p) of finding the
particle there at that point.
 Case (1): when n = 1
h2 2 πx
E1 = and Ψ1 (x) = sin
8mL2 𝐿 𝐿

Hence, Ψ1 (x) is maximum at exactly at the middle of the box.

 Case (2): when n = 2
4h2 2 2π x
E2 = and Ψ2 (x) = sin
8mL2 𝐿 𝐿
Dr. Gounder Thangamani Jayaram
Hence, Ψ2 (x) is maximum at quarter distance from either side of the99box.
 Case (3): when n = 3
9h2 2 3π x
E3 = and Ψ3 (x) = sin
8mL2 𝐿 𝐿
The first three Eigen function Ψ1 , Ψ2 , Ψ3 together with the probability
densities Ψ1 2 , Ψ2 2 , Ψ3 2 are shown in Fig. 1(a) and Fig. 1(b).

100
 Operators:

Dr. Gounder Thangamani Jayaram 101

Eigen operator and Eigenvalue:

102
Dr. Gounder Thangamani Jayaram
Postulates of quantum mechanics:

Dr. Gounder Thangamani Jayaram 103

 104
Dr. Gounder Thangamani Jayaram
 105
Dr. Gounder Thangamani Jayaram
Postulate 3:

Dr. Gounder Thangamani Jayaram 106

 107
Dr. Gounder Thangamani Jayaram
Tunneling Effect
 In classical mechanics, an incident particle with energy (E) coming from the left
collides with the potential barrier (i.e., barrier height (𝑉0 )).
 The energy (E) of the incident particle is assumed to be lower than the top of the
barrier height (i.e., E < 𝑉0 ), than the particle cannot penetrate a barrier and it must
rebound from the barrier.
 So according to the classical mechanics the particle is completely reflected by the
potential barrier.

108
Dr. Gounder Thangamani Jayaram
 In Quantum mechanics, when the energy (E) of the incident particle is less than the
height of the potential barrier (i.e., E < 𝑉0 ), then also particle can penetrate through
the potential barrier.
 So according to quantum mechanics, the particle will be reflected with some
probability, but the other particle can penetrates through the potential barrier and
pass through into the right-hand side region to proceed to the far right.
 This is called Tunneling Effect.

Figure.1: Quantum tunneling through a barrier. The

energy of the tunneled particle is the same but the
amplitude is decreased.
109
Dr. Gounder Thangamani Jayaram
Dr. Gounder Thangamani Jayaram 110
Scanning Tunneling Microscope (STM):
 The scanning tunneling microscope (STM) was invented by Binnig and Rohrer at IBM Zurich (Nobel
prize in Physics in 1986).

 The STM is based on the concept quantum mechanics phenomenon which explains the tunneling
effect.
 Quantum mechanics explains the wave and particle like behavior of tiny particles like photons and
electrons.

 Wavelike properties of electrons permit them to “tunnel” beyond the surface of a solid into the regions of
space that are forbidden to them under the rules of classical physics.
 Smaller the barrier width more precisely wave can pass through.
 Scanning tunneling electron microscope (STM) uses electron tunneling to produce images of
surfaces down to the scale of individual atoms.

111
Dr. Gounder Thangamani Jayaram
Dr. Gounder Thangamani Jayaram 112
Dr. Gounder Thangamani Jayaram 113
Dr. Gounder Thangamani Jayaram 114
Working principle of STM:
 The basic principle used in Scanning Tunneling Microscope (STM)
is the tunneling of the electron between the sharp metallic
conducting tip made up of tungsten metal or a platinum-iridium alloy
acting as an anode probe and the surface of the sample is acting as a
cathode probe.
 Here, constant tunneling current is maintained by adjusting the
distance between the tip and the sample, with an air gap for electron
to tunnel.
 In a similar manner the tip is used to scan atom by atom and line by
line the surface of the sample, and the topography of the sample is
recorded in the computer. Dr. Gounder Thangamani Jayaram
115
Construction of the STM:
Figure shows the schematic diagram of a typical STM. It essentially consists of the following
parts:

116
Dr. Gounder Thangamani Jayaram
 117
Dr. Gounder Thangamani Jayaram
Dr. Gounder Thangamani Jayaram 118
Dr. Gounder Thangamani Jayaram 119
Working of the STM:

 STM tips are usually made from tungsten metal or platinum-iridium alloy, and at
the very end of the tip (called apex) there is one atom of the material.
 Scanning tip is the most important aspect of the STM as tunneling current is carried
by that particular atom.
 A bias voltage ranging from 1 mV to 1 V is applied, and the tip is brought close to
the sample by controlling the voltages for piezoelectric scanner, which is turned off
when the tip and sample are sufficiently close.
 Above the specimen surface there is an electron cloud due to the surface atoms, and
when the tip is brought near to 1 nm of the sample surface, electrons can penetrate
across the gap, causing a current flow that can be measured.
 However, the tip and sample separation gap width (L) is typically maintained in the
range of 4 -7 Ao (0.4 – 0.7 nm).
Dr. Gounder Thangamani Jayaram 120
 The electron transmission probability is proportional to e-L, where L is the gap width, so
even a small change in L means a detectable change in the tunneling current.
 If the tip is moved across the sample in the X-Y plane, the changes in surface height and
density of states cause changes in current.
 The variation in tunneling current gives an image of the surface atoms of the specimen.
 The scanning is done in anyone of the two modes: 1. Constant height mode. Or
2. Constant current mode.

121
Dr. Gounder Thangamani Jayaram
 1: Constant height mode.

 If the probe scans the surface at a constant height, the tunneling current fluctuates
as the tip passes over different atoms.
 Depending upon the nature of atom (and associated electrons cloud) the tunneling
current varies and the image recorded gives the atom by atom variation over the
specimen. This is constant height mode (Figure).
 Constant height mode is faster, as the piezoelectric movements require more time
to register the height change in constant current mode than the current changes in
constant height mode.

122
Dr. Gounder Thangamani Jayaram
 2: Constant current mode.
 As the tunneling current changes feedback electronic current changes the height of
the probe above the specimen surface by adjusting the voltage of piezoelectric
height control mechanism to get constant current.
 Generally, the tunneling current changes exponentially with distance between
probe and specimen surface.
 For a change of gap by about 0.1 nm, current changes by a factor of 10.

 For the same reason, it is a disadvantage,

if the surface is contaminated.
 Another limitation is that the specimen
must have a conducting surface for the
tunneling current to flow.
 STM cannot be used to image the
insulating materials.
123
Dr. Gounder Thangamani Jayaram
Application of STM:

 To obtain atomic scale images of metal surface.

 It provides 3D profile of the surface which is very useful for

characterizing surface roughness and observing surface defects.

 In chemistry, surface of organic molecules and their structures can

be studied.

Dr. Gounder Thangamani Jayaram 124