UNIT I and II

Quantum Mechanics
&
Quantum Statistics
 Introduction : Black Body Radiation
 A blackbody is an idealized object which absorbs and emits all frequencies.
Classical physics can be used to derive an equation which describes the
intensity of blackbody radiation as a function of frequency for a fixed
temperature — the result is known as the Rayleigh-Jeans law. Although the
Rayleigh-Jeans law works for low frequencies, it diverges as f2; this
divergence for high frequencies is called the ultraviolet catastrophe.
 In 1896 Wien derived a distribution law of radiation. Planck, who was a
colleague of Wien's when he was carrying out this work, later, in 1900,
based quantum theory on the fact that Wien's law, while valid at high
frequencies, broke down completely at low frequencies.
 All objects with a temperature above absolute zero (0 K, -273.15 oC) emit
energy in the form of electromagnetic radiation.
A blackbody is a theoretical or model body which absorbs all radiation
falling on it, reflecting or transmitting none. It is a hypothetical object
which is a “perfect” absorber and a “perfect” emitter of radiation over all
wavelengths.
 The spectral distribution of the thermal energy radiated by a blackbody (i.e.
the pattern of the intensity of the radiation over a range of wavelengths or
frequencies) depends only on its temperature. Blackbody radiation curves
at several different temperatures.
 In the image above, notice that:
 The blackbody radiation curves have quite a complex shape (described by
Planck’s Law).
 The spectral profile (or curve) at a specific temperature corresponds to a
specific peak wavelength, and vice versa.
 As the temperature of the blackbody increases, the peak wavelength
decreases (Wien’s Law).
 The intensity (or flux) at all wavelengths increases as the temperature of the
blackbody increases.
 The total energy being radiated (the area under the curve) increases rapidly
as the temperature increases (Stefan–Boltzmann Law).
 Although the intensity may be very low at very short or long wavelengths,
at any temperature above absolute zero energy is theoretically emitted
at all wavelengths (the blackbody radiation curves never reach zero).
 The characteristics of blackbody radiation can be described in terms of several laws:
 1. Planck’s Law of blackbody radiation, a formula to determine the spectral energy
density of the emission at each wavelength (Eλ) at a particular absolute temperature
(T).
 2. Wien’s Displacement Law, which states that the frequency of the peak of the
emission (fmax) increases linearly with absolute temperature (T). Conversely, as the
temperature of the body increases, the wavelength at the emission peak decreases.
 3. Stefan–Boltzmann Law, which relates the total energy emitted (E) to the
absolute temperature (T).
 Planck’s Law: Assumptions:1. A cavity in a material that is maintained at
constant temperature T. The emission of radiation from the cavity walls is in
equilibrium with the radiation that is absorbed by the walls.The radiation field in an
empty volume in thermal equilibrium with a container at T can be viewed as a
superposition of standing harmonic waves. The radiation field in an empty volume
(V=L3) is in thermal equilibrium with container at temperature T.
 2. Planck assumed that the sources of radiation are atoms in a state of
oscillation and that the vibrational energy of each oscillator may have any
of a series of discrete values but never any value between. Planck further
assumed that when an oscillator changes from a state of energy E1 to a state
of lower energy E2, the discrete amount of energy E1 − E2, or quantum of
radiation, is equal to the product of the frequency of the radiation,
symbolized by the Greek letter ν and a constant h, now called Planck’s
constant, that he determined from blackbody radiation data;
i.e., E1 − E2 = hν.
Derivation of Planck’s Radiation Law:
 Let N be the total number of vibrating oscillators & E be their energy, then
average energy of these oscillators is given by
<E> = Etot./Ntot
 if is the number of oscillators with zero energy (in the so-called
ground-state), then the numbers in the 1st, 2nd, 3rd etc. levels () are given
by
 But, as E=nhν, we can write

To make it easier to write, we are going to substitute,

so we have,

The total number of oscillators is given by

Remember, this is the number of oscillators at each frequency, so the energy

at
each frequency is given by the number at each frequency multiplied by the
energy of each oscillator at that frequency. So

which we can now write as

The total energy is given by

The average energy <E> is given by

where

Then

The number of modes in the frequency interval ν to ν +dν is given by

(8πν2/c3 ) dν per unit volume. (By Rayleigh Jeans law.)
 The energy density of radiation in the frequency range ν to ν +dν is

u(ν) dν = <E> x No. of modes

u(ν) dν = 8πhν3___ dν __
c 3 [exp (hν/kT) − 1]
This is the Planck distribution function.
In terms of wavelength Planck’s radiation formula can be given as
 Matter Waves

1. According to Plank’s quantum theory, energy is emitted in the form of

packets or quanta called Photons.

2. According to Plank’s law, the energy of photons per unit volume in black
body radiation is given by
Eλ=8πһс∕λ5[exp(h‫ט‬/kT) -1]

 According to Louis de Broglie since radiation such as light exhibits dual

nature both wave and particle, the matter must also posses dual nature.
 The wave associated with matter called matter wave has the wavelength
λ=h/m‫ ט‬and is called de Broglie wavelength
 Characteristics of matter waves
Since λ=h/m‫ט‬,
1. Lighter the particle, greater is the wavelength associated with it.
2. Lesser the velocity of the particle, longer the wavelength associated with it.
3. For v=0, λ=∞. This means that only with moving particle matter wave is
associated.
4. Whether the particle is charged or not, matter wave is associated with it. This
reveals that these waves are not electromagnetic but a new kind of waves.
5. No single phenomena exhibits both particle nature and wave nature
simultaneously.
6. While position of a particle is confined to a particular location at any time, the
matter wave associated with it has some spread as it is a wave. Thus the wave
nature of matter introduces an uncertainty in the location of the position of the
particle. Heisenberg’s uncertainty principle is based on this concept.
 deBroglie hypothesis :
The dual nature of light possessing both wave and particle properties was explained by
combining Plank’s expression for the energy of a photon E = h ν with Einstein’s mass
energy relation E = m c2 (where c is velocity of light , h is Plank’s constant , m is
mass of particle )
h ν = m c2
Introducing ν = c / λ, we get h c / λ = m c2
==> λ = h / mc = h / p where p is momentum of particle
λ is deBroglie wavelength associated with a photon.
deBroglie proposed the concept of matter waves , according to which a material
particle of mass ‘m’ moving with velocity ‘v’ should be associated with deBroglie
wavelength ‘λ’ given by

λ =h/mv=h/p
The above eqn. represents deBroglie wave eqn.
 The Phase Velocity
The phase velocity is the wavelength / period: v = λ/ t
Since f = 1/t : v = l f
In terms of k, k = 2p / λ, and
the angular frequency, w = 2p / t, this is:
v =w/k
Davisson-Germer Experiment
 In order to test de Broglie’s hypothesis that matter behaved like waves,
Davisson and Germer set up an experiment very similar to what might be
used to look at the interference pattern from x-rays scattering from a crystal
surface. The basic idea is that the planar nature of crystal structure provides
scattering surfaces at regular intervals, thus waves that scatter from one
surface can constructively or destructively interfere from waves that scatter
from the next crystal plane deeper into the crystal. Their experimental
apparatus is shown below

Figure shows experimental arrangement for electron diffraction.

 Apparatus
 Electron gun.
 Nickel crystal.
 Electron detector/collector.
 Working
 Electron gun has tungsten filament coated with barium oxide for high
emission efficiency. When this filament is heated it emits thermal electrons.
The electrons are accelerated by cylindrical shield kept at fixed known high
positive voltage (V). The electrons emerge out of shield as fine beam and
its energy can be calculated using value of voltage applied. This beam is
made to fall on the surface of nickel crystal. The electron beam gets
reflected after hitting the nickel crystal. The intensity of reflected electrons
in a particular direction is measured by the electron collector, which can be
moved on a circular scale. The collector provides the value of current which
is proportionate to the number of electrons incident on it.The intensity of
reflected electron beam is recorded for different angles of deflection (Φ)
and different velocities of electrons which is measured by applied voltage
(V).A radial graph is plotted to observe the results of recorded data. It is
observed that, current is maximum when deflection angle Φ = 50° and
accelerating voltage V = 54V.
 According to Bragg’s diffraction formula −
 Path difference = wavelenght i.e. asinθ = λ
 Where, a = opening for wave to enter. λ = Wavelength
But in Davisson and Germer’s experiment,
Path difference = 2dsinθ
∴ 2dsinθ = λ
Where, d = Spacing between atomic planes. λ = wavelenght
θ = Glancing angle. For nickel crystal spacing between atomic planes is d =
0.91 × 10-10, For deflection angle Φ = 50o , Glancing angle is θ = 65o as
−glancing angle = 90o − Φ/2
Therefore,
λ = 2 × 0.91 × 10-10 × sin(65) = λ = 1.65A
By using de Broglie’s wavelength of electron at accelerating voltage 54V is
given by − λ = 12.27√vA = 12.27√54 = 1.66A
This confirms the wave nature electron and proves that materials have dual
nature.
 Group Velocity

This is the velocity at which the overall shape of the wave’s amplitudes, or the
wave ‘envelope’, propagates. (= signal velocity)
Here, phase velocity = group velocity (the medium is non-dispersive)
 Phase Velocity
The distinction between the phase velocity and the group velocity of a wave is a
concept of general signicance for many different waves in physics: electromagnetic
waves, particle waves, elastic waves and so on. We start by considering a general one-
dimensional wave
A(x; t) = A0e i(kx-ωt)
where A0 is the amplitude, k the wave number, ω is the angular frequency, and t
the time. The important thing to note is that ω depends on the wave number k
or the wavelength λ= 2П/k. This phenomenon is called dispersion and it might
be familiar from optics, where the speed of light in a material (or the index of
refraction) depends on the wavelength.

Starting from the dispersion ω(k), we derive the phase velocity as

vp = ω /k
and the group velocity as
vg =d ω /dk
Albert Einstein first explained the wave–particle duality of light in 1905. Louis de
Broglie hypothesized that any particle should also exhibit such a duality. The velocity
of a particle, he concluded then (but may be questioned today, see above), should
always equal the group velocity of the corresponding wave. De Broglie deduced that if
the duality equations already known for light were the same for any particle, then his
hypothesis would hold. This means that

where E is the total energy of the particle, p is its momentum, ħ is the reduced Planck
constant. For a free non-relativistic particle it follows that

where is the mass of the particle and v its velocity.

where m is the mass of the particle, c is the speed of light in a vacuum, γ is the Lorentz
factor, and v is the velocity of the particle regardless of wave behavior.
Group velocity (equal to an electron's speed) should not be confused with phase
velocity (equal to the product of the electron's frequency multiplied by its wavelength).
Both in relativistic and non-relativistic quantum physics, we can identify the group
velocity of a particle's wave function with the particle velocity. Quantum mechanics
has very accurately demonstrated this hypothesis, and the relation has been shown
explicitly for particles as large as molecules
 PHOTOELECTRIC EFFECT
In photoelectric effect, electrons are emitted from matter (metals and non-
metallic solids, liquids or gases) as a consequence of their absorption of energy
from electromagnetic radiation of very short wavelength and high frequency,
such as ultraviolet radiation.
 MATHEMATICAL DESCRIPTION

The maximum kinetic energy of an ejected electron is given by:

Kmax = hf –Ф
where h is the Planck constant and f is the frequency of the incident photon. The
term Ф = is the work function which gives the minimum energy required to
remove a delocalized electron from the surface of the metal. The work function
satisfies Ф=hf0

where f0is the threshold frequency for the metal. The maximum kinetic energy of an
ejected electron is then

Kmax = hf –hf0
Kinetic energy is positive, so we must have f>f0for the photoelectric effect to occur.
 COMPTON EFFECT
Compton scattering is an inelastic scattering of a photon by a free charged
particle, usually an electron. It results in a decrease in energy (increase in
wavelength) of the photon (which may be an X-ray or gamma ray photon), called
the Compton effect. Part of the energy of the photon is transferred to the
scattering electron. Inverse Compton scattering also exists, in which a charged
particle transfers part of its energy to a photon.
 MATHEMATICAL DESCRIPTION

ENERGY CONSERVATION

Energy of photon before collision = E1 = hu1

Energy of electron before collision = E2 = moc2
Energy of photon after collision = E1`= hu 2
Energy of electron after collision = E2` = mc2

Since the collision between photon and electron is elastic. Therefore energy and
momentum will be conserved.

Total energy before collision = Total energy after collision

E1 + E2 = E1` + E2`
hu1 + moc2 = hu2 + mc2
hu1 - hu2 = mc2 – moc2
h(u - u ) = c2(m – m )……………….(1)
MOMENTUM CONSERVATION

Momentum of photon before collision = h /l1

Momentum of electron before collision = 0
Momentum of photon after collision = h / l2
Momentum of electron after collision = mv
MOMENTUM EQUATION ALONG X-AXIS

h/l1 + 0 = h/l2Cosq + mvCosf

h/l1 = h/l2Cosq + mvCosf………….(2)
MOMENTUM EQUATION ALONG Y-AXIS

0 + 0 = h/l2Sinq + (-mvSinf)
h/l2Sinq -mvSinf = 0……………….(3)
Solving (1) , (2) and (3), we get the following result:
1/u2 – 1/u1 = h/moc2 (1- Cosq) ………….(4)
c(1/u2 – 1/u1) = hc/moc2 (1- Cosq)
c/u2 – c/u1 = h/moc (1- Cosq)
But c/u = l, therefore,

l2 - l1 = h/moc (1- Cosq)

where l2 - l1 = Compton’s shift in wavelength

h/moc is called Compton’s wavelength and its value is
2.426X10-12 m
 Heisenberg's uncertainty principle
•The uncertainty principle states that the position and velocity cannot
both be measured,exactly, at the same time (actually pairs of position,
energy and time)
•uncertainty principle derives from the measurement problem, the
intimate connection between the wave and particle nature of quantum
objects.
•the change in a velocity of a particle becomes more ill defined as the
wave function is confined to a smaller region.
Mathematically we describe the uncertainty principle as the following, where `x' is
position and `p' is momentum:

This is perhaps the most famous equation next to E=mc2 in physics. It basically says
that the combination of the error in position times the error in momentum must
always be greater than Planck's constant. So, you can measure the position of an
electron to some accuracy, but then its momentum will be inside a very large
range of values. Likewise, you can measure the momentum precisely, but then its
position is unknown.Notice that this is not the measurement problem in another
form, the combination of position, energy (momentum) and time are actually
undefined for a quantum particle until a measurement is made (then the wave
function collapses).
Also notice that the uncertainty principle is unimportant to macroscopic objects
since Planck's constant, h, is so small (10-34). For example, the uncertainty in
position of a thrown baseball is 10-30 millimeters.
The depth of the uncertainty principle is realized when we ask the question; is our
knowledge of reality unlimited? The answer is no, because the uncertainty
principle states that there is a built-in uncertainty, indeterminacy, unpredictability
to Nature.
Heisenberg Example: Electron can not
Confined in the Nucleus
The uncertainty principle contains implications about the energy that would be
required to contain a particle within a given volume. The energy required to contain
particles comes from the fundamental forces, and in particular the electromagnetic
force provides the attraction necessary to contain electrons within the atom, and
the strong nuclear force provides the attraction necessary to contain particles within
the nucleus. But Planck's constant, appearing in the uncertainty principle, determines
the size of the confinement that can be produced by these forces. Another way of
saying it is that the strengths of the nuclear and electromagnetic forces along with
the constraint embodied in the value of Planck's constant determine the scales of the
atom and the nucleus.
The following very approximate calculation serves to give an order of magnitude for
the energies required to contain particles.
The Time-Independent Schrödinger Equation
We start with the one-dimensional classical wave equation,

By introducing the separation of variables

we obtain

If we introduce one of the standard wave equation solutions for f(t)

Now we have an ordinary differential equation describing the spatial amplitude

of the matter wave as a function of position. The energy of a particle is the sum
of kinetic and potential parts
which can be solved for the momentum, to obtain

Now we can use the de Broglie formula to get an expression for the wavelength

if ω = 2πν then

we obtain the famous time-independent Schrödinger equation

Schrodinger Time Dependent: A Wave Equation for Electrons

(free-particle)

This is time-Independent Schrodinger Wave Equation

 Physical significance of Wave function Ψ

1. The wave functions Ψn and the corresponding energies En, which are often
called eigen functions and eigen values respectively, describe the quantum
state of the particle.

2.The wave function Ψ has no direct physical meaning. It is a complex quantity

representing the variation of matter wave. It connects the particle nature and
its associated wave nature.
3. ΨΨ* or |Ψ|2 is the probability density function. ΨΨ*dxdydz gives the
probability of finding the electron in the region of space between x and
x+dx, y and y+dy and z and z+dz.If the particle is present

∫ΨΨ*dxdydz=1

4. It can be considered as probability amplitude since it is used to find the

location of the particle.
 Schrodinger developed a differential equation whose solutions yield the

possible wave functions that can be associated with a particle in a given

situation.
Schrödinger wave equation
The equation tells us how the wave function changes as a result of forces
acting on the particle.
The one dimensional time independent Schrödinger wave equation is given
by
d 2Ψ/dx2 + [2m(E-V)/ ћ2] Ψ=0
(or)
d 2Ψ/dx2+ [8π2m(E-V) / h2] Ψ=0

This equation is popularly known as schrodinger equation .

 Particle in one dimensional potential box

Quantum mechanics has many applications in atomic physics.

Consider one dimensional potential well of width L.
Let the potential V=0inside the well and V= ∞outside the well.
Substituting these values in Schrödinger wave equation and simplifying we
get the energy of the nth quantum level,
En=(n2π2ћ2)/2mL2=n2h2/8mL2
When the particle is in a potential well of width L, Ψn=(√2/L)sin(nπ/L)x & En
= n2h2/8mL2,n=1,2,3,….
When the particle is in a potential box of sides Lx,Ly,Lz Ψn=(√8/V)sin(nx π/Lx)

x sin (ny π/Ly) ysin (nz π/Lz)z.

Where nx, ny or nz is an integer under the constraint n2= nx2+ny2+ nz 2.

Finite well, Tunneling and
SHO
PPT - The Schrödinger Wave Equation
PowerPoint Presentation, free download -
ID:1585709 (slideserve.com)
 Classical statistics

In classical mechanics all the particles (fundamental and composite particles, atoms,

molecules, electrons, etc.) in the system are considered distinguishable. This means

that one can label and track each individual particle in a system. As a consequence

changing the position of any two particles in the system leads to a completely

different configuration of the entire system. Furthermore there is no restriction on

placing more than one particle in any given state accessible to the system. Classical

statistics is called Maxwell–Boltzmann statistics (or M–B statistics).

 Quantum statistics

The fundamental feature of quantum mechanics that distinguishes it from classical

mechanics is that particles of a particular type are indistinguishable from one
another. This means that in an assembly consisting of similar particles,
interchanging any two particles does not lead to a new configuration of the system
Bose–Einstein
(in the language of quantum mechanics: statistics
the wave function of the system is invariant
with respect to the interchange of the constituent particles). In case of a system
consisting of particles belonging to different nature (for example electrons and
protons), the wave function of the system is invariant separately for the assembly of
the two particles.

While this difference between classical and quantum description of systems is

fundamental to all of quantum statistics, it is further divided into the following two
classes on the basis of symmetry of the system.
 Bose–Einstein statistics

In Bose–Einstein statistics (B–E Statistics) interchanging any two particles of the

system leaves the resultant system in a symmetric state. That is, the wave function
of the system before interchanging equals the wave function of the system after
interchanging.

Fermi–Dirac statistics

In Fermi–Dirac statistics (F–D statistics) interchanging any two particles of the

system leaves the resultant system in an anti symmetric state. That is, the wave
function of the system before interchanging is the wave function of the system after
interchanging, with an overall minus sign.
 Bose-Einstein Distribution

The Bose-Einstein distribution describes the statistical behavior of integer spin

particles (bosons). At low temperatures, bosons can behave very differently than
fermions because an unlimited number of them can collect into the same energy
state, a phenomenon called "condensation".
 Fermi-Dirac Distribution
The Fermi-Dirac distribution applies to fermions, particles with half-integer spin
which must obey the Pauli exclusion principle. Each type of distribution function
has a normalization term multiplying the exponential in the denominator which may
be temperature dependent. For the Fermi-Dirac case, that term is usually written:

The significance of the Fermi energy is most clearly seem by setting T=0. At
absolute zero, the probability is =1 for energies less than the Fermi energy and zero
for energies greater than the Fermi energy. We picture all the levels up to the Fermi
energy as filled, but no particle has a greater energy. This is entirely consistent with
the Pauli exclusion principle where each quantum state can have one but only one
particle.
Applications of Statistics

Unit-14.pdf (egyankosh.ac.in)
 Assignments
Q. No.1. Why don’t hot objects emit more ultraviolet light than
they do?
Q. No.2. What is Photon ?
Q.No. 3. How come I’ve never seen a photon?
Q. No.4. What is quantum wavelength of an object ?
Q.No.5. How the mathematical machinery of quantum mechanics
is turned to the hydrogen atom, the solutions yield energy levels
in exact agreement with the optical spectrum. Explain.
Q.No. 6. Explain uncertainty in energy & time.
Q.No. 7. What is tunneling effect ?
Q.No. 8. Define Bosons & fermions.
Q.No. 9. Establish relation between phase velocity & group
velocity in dispersive medium.
Q.No. 10. Write S.W. equation for a particle in One-D box.
Tutorial Sheet
1. Black body radiation and Planck’s law: Consider a black body
maintained at the temperature T . According to Planck’s radiation law, the
energy per unit volume within the frequency range ν and ν + dν associated
with the electromagnetic radiation emitted by the black body is given by
uν dν =8 π hν3 dν /c3exp (h ν/kB T ) − 1
where h and kB denote the Planck and the Boltzmann constants,
respectively, while c represents the speed of light.
Arrive at the Wien’s law, viz. that λMAX T = b = constant, from the above
Planck’s radiation law. Note that λMAX denotes the wavelength at which the
energy density of radiation from the black body is the maximum.
Find the total energy emitted by the black body is described by the integral
0 to ∞, Using the above expression for uν , evaluate the integral and show
that u = 4cσ/ T 4.
2. Consider the emission of electrons due to photoelectric effect from a zinc
plate. The work function of zinc is known to be 3.6 eV. What is the maximum
energy of the electrons ejected when ultra-violet light of wavelength 3000 A is
incident on the zinc plate?
3. Consider a quantum mechanical particle propagating in a given potential and
described by the wave function Ψ(x, t). The probability P (x, t) of finding the
particle at the position x and the time t is given by
P (x, t) = |Ψ(x, t)|2.
Using the one-dimensional Schrodinger equation, show that the probability P
(x, t) satisfies the conservation law
∂P (x, t) + ∂j(x, t) = 0/∂t ∂x
where the quantity j(x, t) represents the conserved current given by
j(x, t) = 2 i m
4 Consider a particle in the infinite square well. Let the initial wave function of
the particle be given by
Ψ(x, 0) = A [ψ1(x) + ψ2(x)] ,
where ψ1(x) and ψ2(x) denote the ground and the first excited states of the
particle.
a) Normalize the wave function Ψ(x, 0).
b) Obtain the wave function at a later time t, viz. Ψ(x, t), and show that the
probability |Ψ(x, t)|2 is an oscillating function of time.
c) Evaluate the expectation value of the position in the state Ψ(x, t) and show
that it oscillates. What are the angular frequency and the amplitude of the
oscillation?
d) What will be the values that you will obtain if you measure the energy of
the particle? What are the probabilities for obtaining these values?
e) Evaluate the expectation value of the Hamiltonian operator corresponding to
the particle in the state Ψ(x, t). How does it compare with the energy eigen
values of the ground and the first excited states?