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UNIT 4 QUANTUM MECHANICS

PHY110

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Need of quantum mechanics
To overcome the limitation of classical mechanics

Classical mechanics failed to explain….

` 1) Stability of atom
2) Spectral distribution of black body radiation
Planck’s quantum hypothesis
3) Origin of discrete spectra of atoms
4) Photoelectric effect
particle nature of light by Einstein
5) Crompton effect
6) Raman effect

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1. Black body radiation and Planck’s hypothesis

1. Atomic oscillator
Planck’s law 2. Quanta of energy

✓ Rayleigh-Jeans can be deduced from Planck’s law for low frequency (large
wavelength) and high temperature
✓ Similarly Wien’s law can be deduced from Planck’s law for high frequency (low
wavelength) and low temperature
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2. Photoelectric effect
Discovered by Hertz but explained by Einstein
Kinetic energy of the ejected electron Ek

Work
function
Incident
photon energy
This effect says about the emission/ejection
of electrons from the metal surface upon
irradiation with light waves
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❑ We knew the wave nature of light or electromagnetic radiation

with the help of Maxwell’s equation- electromagnetic theory
❑ Then assumed particle nature of light with the Planck’s black
body radiation
❑ With Einstein’s photoelectric equation we experimentally
proved particle nature of light
✓ Importance of quantum mechanics and quantum/particle
nature of light

Wave nature of particles?? A mathematical relation connecting

wavelength () to momentum (p) De Broglie!

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 Nature loves symmetry!!

1. Concept of de Broglie matter waves

➢ Dual nature of radiation...the fact that ignited de Broglie’s curiosity
➢ Dual nature of matter - de Broglie’s imagination

2. Wavelength of matter waves in different forms

➢ Relation between wavelength and momentum/energy…

We saw the particle nature of electromagnetic radiation , Now we

see the wave nature of particle (matter)

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 What we know about particle and wave

Concept of particle Concept of wave

i. Mass: has definite mass
i. Phase of wave velocity: Phase gives
ii. Position; located to a place or point instantaneous position and direction
iii. Velocity: move with certain velocity ii. Frequency and wavelength: main
iv. Momentum (p): mass and velocity so characteristics of a wave
it has momentum
iii. Amplitude: Gives the intensity of the
v. Energy (E): it has PE, KE and rest-mass disturbance in the medium
energy

❖ E and p are the

characteristics of the particle ❖  and  are the characteristics of
the wave

Can we find a mathematical formulation to connect these two?

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 Is it Possible? Can we put it in a mathematical
relation

If we think about wave and particle in the above description, it is very difficult accept the
wave-particle duality rt?
Superposition of wave? Yes
Superposition of particle? No..two particles can not have same position at the same time

If we can assign these

If we can assign these, i. Mass: difficult to think mass being
i. Phase of wave velocity: associated with a wave..
ii. Frequency and wavelength: ii. Energy
Then matter can be considered as wave iii. Momentum
as well iv. Velocity
Then, a wave can be considered as particle
as well

We will see that now for the radiation first!

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 Dual nature of radiation
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In the case of radiation (Plank’s theory), we know Energy,

Now will go to Einstein special theory of relativity and that famous

equation De Broglie hypothesized that the two energies would be equal

But mc is nothing but the momentum of photon,

.. by mixing Einstein’s famous matter-energy relation with Planck’s famous

quantum oscillator theory.. Wavelength of the wave is related to the momentum
of its particle through the Planck’s constant ..

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 Dual nature of radiation

From the same equation of energy, we have we can have

the relation for the mass of photon,
the photon has no rest mass but does have
relativistic mass

So photons has mass ( ), momentum ( ), energy ( )

wavelength ()and frequency ()

This was proposed by de Broglie in 1923 in his doctoral thesis

Since E, m and P are particle characteristics, and we got it for radiation, a wave
having wavelength and frequency!! The dual nature has a mathematical basis
now for radiation..

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 Dual nature of MATTER
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If a wave can be so then why not a particle?

de Broglie extended matter concept of radiation and applied to particles as well..
Because real particles do not travel at the speed of light, De Broglie used
velocity (v) for the speed of light (c).

 is the de Broglie wavelength of the matter

wave of the particle moving with velocity v
and momentum p

The de Broglie wavelength is the wavelength, λ, associated with a massive particle

and is related to its momentum, p, through the Planck constant, h: In other words,
you can say that matter also behaves like waves.
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Dual nature of MATTER- de Broglie wavelength
 can be expressed in various ways, depending on the process by which the
particle gain energy for the travel

1. If particle is accelerated through the kinetic energy

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 Dual nature of MATTER- de Broglie wavelength

2. If a charged particle having charge (q) is accelerated through electrostatic

potential V, then the kinetic energy is expressed as

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 Dual nature of MATTER- de Broglie wavelength

3. If the particle having mass (m) is accelerated by means of thermal energy

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4. If the particle having rest mass (m0) is moving with a velocity(v)
comparable to the speed of light (c)

In this case mass is not constant, and relativistic equation come into play and
instantaneous mass is given by

Although de Broglie was credited for his hypothesis, he had no actual experimental evidence
for his conjecture. In 1927, Clinton J. Davisson and Lester H. Germer shot electron particles
onto on to a nickel crystal. What they saw was the diffraction of the electron similar to waves
diffraction against crystals (x-rays). In the same year, an English physicist, George P. Thomson
fired electrons towards thin metal foil providing him with the same results as Davisson and
Germer. PHY110 Q.M
TO CONCLUDE
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1. If particle is accelerated through the kinetic energy

2.If a charged particle having charge (q) is accelerated through electrostatic

potential V

3. If the particle having mass (m) is accelerated by means of thermal energy

4. If the particle having rest mass (m0) is moving with a

velocity(v) comparable to the speed of light (c)

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Davisson-Germer Experiment ➢ Heated filament electron source
➢ Accelerated by applying voltage
➢ Intensity of the scattered electron measured
➢ As function of accelerating voltage
➢ As function of angle 
➢ Plotted in form of polar diagram

Maximum scattering intensity is ++=180°

observed for =50° 2 +50°=180°; =65°
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 If it is due to electron diffraction ( a wave phenomenon) then
Bragg’s law should be satisfied for the glancing angle =65°

For nickel crystal d =0.91Å and for first order diffraction n=1
=2x 0.91Åx sin65°= 1.65Å
Now we have to calculate the de Broglie wavelength of the electron
accelerated with an voltage 54 V
Here q is e – , electron charge and V=54 V

So de Broglie wavelength of electron for

54V acceleration is 1.67 Å.
Comparable with the experimentally determined wavelength
(1.65Å) of wave using wave diffraction experiment
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 Properties of matter-wave

i. Lighter particles have large de Broglie wavelength than heavier one

ii. Smaller the velocity of the particle, the greater is the de Broglie wavelength
associated with it
iii. Matter waves (A wave is associated with each moving particle, e.g., a beam
of electrons can be diffracted just like a beam of light or water wave.) are
generated only when particle is in motion. [ v=0, = ∞]
iv. Matter waves are not electromagnetic ..i.e. independent of charge
v. Velocity of the matter-wave is not constant. It depends on the velocity of
the particle, while velocity of the electromagnetic wave is constant

➢ Velocity of matter wave may be greater than the velocity of light.

Difficult to believe and hence phase velocity and group velocity came
into play..
➢ Wave-particle duality introduce the concept of uncertainty, This
concept suggest that if the particle nature of the matter becomes
certain, the wave nature becomes uncertain and vice versa.
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 phase and group velocities

1) Velocities associated with de Broglie wave

i. Phase or wave velocity (vp)
ii. Group velocity (vg).. Wave packet
iii. Particle velocity (v)

Analogy: city marathon runners

❑ Initially it would appear that all of them are running at the same speed. As time
passes, group spreads out (disperses)
❑ because each runner in the group is running with different speed.
❑ If you think of phase velocity to be like the speed of an individual runner, then
the group velocity is the speed of the entire group as a whole.

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 Phase or Wave Velocity
(vp)
A wave travelling in the +x direction is given by

1
Where a is the amplitude, ω (=2) is the angular frequency and
k (=2/) is the propagation constant
By definition the ratio of the angular frequency to the propagation
constant is the phase velocity, vp
Now we will see why vp it is called wave
velocity also ?

In equation 1, (ωt-kx) is called the phase of the wave

motion. And is a constant for plane wave
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Phase or Wave Velocity (vp)

But dx/dt is the velocity of the wave.. And

same as equation 1. so phase velocity is
nothing but the wave velocity

For an electromagnetic wave

in vacuum.

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 Phase or Wave Velocity (vp)

Phase or Wave Velocity (vp) for de Broglie

wave

We have 2
According to de Broglie 3

From 2 and 3, phase velocity for the de Broglie wave

Since v << c, eqn.(4) implies that phase velocity of de Broglie wave of the particle
is moving with velocity v is greater than c, speed of light!!
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 Group Velocity (vg)

Vg, introduced to overcome the difficulty of vp> c of matter wave: Here each
moving particle is associated with a group of wave or wave packet rather than a
single wave.

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 Group Velocity (vg)

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Eqn.5 has two parts,
(1)A wave with angular frequency ω, propagation constant k and velocity
vp , given by
And is the phase velocity

(2)A nother wave with angular frequency ω, propagation constant k and
velocity vg , given by
And is the group velocity.
Velocity of the wave packet.
Envelop showed by dotted lines in the
figure
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 Group Velocity (vg)

So group velocity is given by

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Now we will find the relation between vp and vg Relation between vp and vg

But

and

That is group velocity is less than the phase velocity in a dispersive medium where vp is a
function of k or .. And for a no-dispervive medium vp is independent of k or , equation 6
gives
because
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 relation between vg and particle velocity (v)

Consider a material particle of rest mass m0. Let its mass be m when moving with
a velocity v. then it energy is given by

We know that

Substitute the value of m from the above into the last two
equation of ω and k

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 relation between vg and particle velocity (v)
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and differentiation with respect to the velocity of the particle v

But Vg is defined as

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 Phase, group & particle velocities

Phase velocity (vp) of the wave is larger than the group velocity (vg) of the waves?

It depends on the nature of the medium.

1) vp = vg for non-dispersive medium- velocity not depend on wave length.
Examples sound waves in air and electromagnetic waves in vacuum.

2) vp >vg for normal-dispersive medium- electromagnetic radiation in medium

where refractive depends on the wavelength and hence velocity of EM changes in the
medium.
3) vp <vg for anomalous-dispersive medium..This we see in matter-wave cases

Now we will see the relation for Phase and group velocities. And
their relationship with the particle velocity (v)

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 UNIT 4 QUANTUM MECHANICS

WAVE FUNCTION & ITS

PHYSICAL SIGNIFICANCE

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 Wave function- classical

………………………………. Eq. 1 is the wave

function… that is the solution of the wave equation

Give value of the physical quantity, E, B or P at a position (x,y,z)

at a given time t.
The uncertainty is only for the microscopic particles -atomic or subatomic particles. So classical
wave equation is not valid for very small particles, like electron, proton, neutron etc..

So we have to modify the wave equation for matter wave.

Before that we have to define our wave function and its properties And we will have
quantum wave equation as a result…
 Wave function- Quantum

Wave function associated with the matter wave is represented by 

➢ This  is not an observable quantity, unlike E and B, P we

have seen in classical wave equation
➢ The value of  is related to the probability of finding the
particle at a given place at a given time.
➢ This wave function  is a complex quantity
➢  exists, its complex conjugate ( *) also exists

This is the probability of finding the particle over all space is unity.
This the normalization condition. Wave function obeys this called
normalisable or normalized.
 Wave function- Quantum

The characteristics of the wave functions in quantum

mechanics are

➢  must be finite, continuous and single valued everywhere

➢  must be normalisable

➢ also must be finite, continuous and single

valued
 Wave function- Quantum

Schrödinger derived a wave equation for matter/wave that would give

wave/particle-like propagation when the wavelength becomes comparatively small.

According to classical mechanics, if a particle of mass m is moving by the action

of force then the total energy E of the particle is the sum of KE and PE,

Schrödinger just changed this classical equation, and we

got the so called quantum wave equation ☺.. We will see
that

Schrodinger’s magic with deBroglie’s matter wave

 Wave function- Quantum

Schrodinger time-independent wave equation

Let us assume a wave associated with a moving particle, (x, y, z) is the position coordinate, (ψ)
is the periodic displacement at any instant of time (t), & (V) is the velocity of that matter-wave.

Differential Eq.1,

, as a periodic displacement in terms of time, Eq.2,

0, as an amplitude of particle-wave at (x, y, z),
independent of (t)

Further, we have a function of (x, y, z), i.e, (r), which is written in vector form
as seen in Eq. 3

Eq.3

Also, Eq. 2 represented can be represented, as seen in Eq.4

Eq.4
Differentiate the Eq.4 twice with time

Eq.5

Substitute Eq.5 in Eq.1, we get

Eq.6 (L.H.S represents eq. with phase

velocity)
 Wave function- Quantum

Schrodinger time-independent wave equation

But we know that, the angular frequency of the wave is related to the wave frequency

Eq.7

Also we know Eq.8

Here, ▼ 2 is the Laplacian operator.

Substitute Eq.7 and Eq.8 in Eq.6 Eq.9

Again from de-Broglie wave concept

Eq.10 And substitute for  in Eq.9

 Wave function- Quantum

Schrodinger time-independent wave equation

Eq.11

Further, if The total energy (E) of the particle is the sum of potential energy
(V) and kinetic energy (½ mv2), so we can write

Eq.12

By using Eq.12 in Eq.11, we get

But we know
 Wave function- Quantum

Schrodinger time-independent wave equation

Eq.13

This is the Time-independent Schrödinger equation, where the  is

known as the wave function

For a freely moving or free particle V=0, so Eq.13 takes the form

This is the Time-independent

Eq.14 Schrödinger equation for a
free particle.

Hence, when a Laplacian and E operate on the wave

function, this is the required wave equation we get.
 Wave function- Quantum

Schrodinger time-dependent wave equation

If we eliminate E from the time-independent Schrödinger equation we get

time-dependent Schrödinger equation?.. For that that we go back to the
wave function (r,t) and differentiate it twice with respect to time
Eq.4 and differentiate it with respect to time

Eq.15

Eq.16

Substitute this equation in in the time independent Schrödinger equation we

derived before Eq.13
 Schrodinger Time-Dependent wave equation

quantum This is the time-dependent Schrödinger

equation
And in terms of the operators

classical p momentum operator

 Physical significance of wave function

By analogy with waves such as those of sound, a wave function, Ψ, may be

thought of as an expression for the amplitude of the particle wave (deBroglie
wave), although for such waves amplitude has no physical significance.

However, the square of the wave function, Ψ, does have physical significance:
the probability of finding the particle described by a specific wave function Ψ
at a given point and time is proportional to the value of Ψ2

Ψ as such has no physical significance, but it is operated with an operator that

‘operation’gives us a significant physical quantity….???
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Infinite Potential Well or Particle in a Box

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 Because Sin n∏ = 0; n =1, 2…

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 Application 1 explanation
Why an electron cannot exist in the nucleus ?

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Why an electron cannot exist in the nucleus?

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