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Module-1
Modern Physics and Quantum Mechanics

Black body radiation spectrum, Assumptions of quantum theory of radiation,Plank‟s

law, Weins law and Rayleigh Jeans law, for shorter and longerwavelength
limits.Wave Particle dualism, deBroglie hypothesis. Compton Effectand its Physical
significance. Matter waves and their Characteristic properties,Phase velocity and
group velocity. Relation between phase velocity and groupvelocity, Relation between
group velocity and particle velocity.
Heisenberg‟s uncertainty principle and its application, (Non-existence
ofelectron in nucleus).Wave function, Properties and physical significance ofwave
function, Probability density and Normalization of wave function.Setting up of one
dimensional time independent Schrodinger wave equation.Eigen values and Eigen
functions. Application of Schrodinger wave equation.Energy Eigen values and Eigen
functions for a particle in a potential well ofinfinite depth and for free particle.

Content:
 Black body radiation spectrum
s

 De Broglie‟s concept of matter waves

 Phase Velocity
 Group velocity
 Relation between phase velocity and group velocity
 Heisenberg uncertainty principle
 Schrodinger wave equation
 Eigen values and Eigen function
 Eigen function
 Particle in potential well of infinite depth

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Blackbody Radiation spectrum:

A Blackbody is one which absorbs the entire radiation incident on it and emits
all the absorbed radiation when it is more hot. A true blackbody does not exist
practically. A blackbody designed by Wein has features very close to the true
blackbody. A blackbody at a particular temperature found to emit a radiation of all
possible wavelengths. It is a continuous spectrum starting from certain minimum

m
wavelength to maximum wavelength. The maximum intensity corresponds to a
particular wavelength. For different temperatures of the black body, there are different

co
curves. As the temperature of the body increases, the wavelength corresponding to
maximum intensity shifts towards lower wavelength side. The distribution of energy

p.
in black body radiation is shown in the following fig.

ou
UV VISIBLE IR

6000K

Energy gr 3000K
2000K
ts
en

Wavelength

Wein‟s, Rayleigh-Jeans and Planck have given their explanations to account these
ud

observed experimental facts as follows:

Wein’s Displacement Law:
st

The law states that “the wavelength of maximum intensity is inversely

proportional to the absolute temperature of the emitting body, because of which the
ity

peaks of the energy curves for different temperatures get displaced towards the lower
wavelength side”.
.c

1
i.e. m    or λmT=constant=2.898×10-3 mK
w

T 
w

Wein showed that the maximum energy of the peak emission is directly
proportional to the fifth power of absolute temperature.
w

Emα T5 or Em = constant × T5

Wein’s law:The relation between the wavelength of emission and the temperature of
the source is

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C 
 2 
U  d  C1  e 5  T 
d

Where Uλdλ is the energy / unit volume in the range of wavelength λ and λ+dλ, C 1
and C2 are constants.
This is called Wein‟s law of energy distribution in the black body radiation
spectrum.
Drawbacks of Wein‟s law:
Wein‟s law holds good for the shorter wavelength region and high temperature
of the source. It failed to explain gradual drop in intensity of radiation corresponding
to longer wavelength greater than the peak value.
1. Rayleigh-Jeans Law:
Rayleigh derived an equation for the blackbody radiation on the basis of

o
principle of equipartition of energy. The principle of equipartition of energy suggests
that an average energy kT is assigned to each mode of vibration. The number of
vibrations/unit volume whose wavelength is in the range of λ and λ+dλ is given by
8πλ-4dλ.
The energy/unit volume in the wavelength range λ and λ + dλ is

Uλd λ = 8πkTλ-4dλ

Where k is Boltzmann constant= 1.38x10-23J/K.

This is Rayleigh-Jeans equation. Accordingly energy radiated by the

blackbody decreases with increasing wavelength.
Drawbacks of Rayleigh-Jeans Law: (or Ultra Violet Catastrophe)

Rayleigh-Jeans Law predicts to radiate all the energy at shorter wavelength

side but it does not happen so. A black body radiates mainly in the infra-red or visible
region of electromagnetic spectrum and intensity of radiation decreases down steeply
for shorter wavelengths. Thus, the Rayleigh-Jeans Law fails to explain the lower
wavelength side of the spectrum. This is referred to as ultra-violet Catastrophe.

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2. Planck’s Law:
Planck assumed that walls of the experimental blackbody consists larger
number of electrical oscillators. Each oscillator vibrates with its own frequency.
i) Each oscillator has an energy given by integral multiple of hυ where h is
Planck‟s constant & υ is the frequency of vibration.
E = nhυ where n = 1, 2, 3 . . . etc.
ii) An oscillator may lose or gain energy by emitting or absorbing respectively a
radiation of frequency υ where υ=ΔE/h, ΔE is difference in energies of the
oscillator before and after the emission or absorption take place.

Planck derived the law which holds good for the entire spectrum of the blackbody
radiation as
8hc  1 
Uλdλ = 5  h / kT
d (since υ = c/λ)
 e 1
This is Planck‟s Radiation Law.

Reduction of Planck’s law to Wein’s law and Rayleigh Jeans law:

1) For shorter wavelengths, υ = c/λ is large.
d

When υ is large, ehυ/kT is very large.

. .. ehυ/kT>> 1
. .. (ehυ/kT-1) ≈ ehυ/kT = ehc/λkT
Substituting in eqn 1:
  C2 
 
Uλdλ =
8h  1 
d = C1 5 e  T 
d
5  e hc/kT 
Where C1 = 8πhc and C2 = hc/k
This is the Wein‟s law of radiation.

2) For longer wavelengths υ = c/λ is small.

When υ is small hυ/kT is very small.
Expanding ehυ/kT as power series:
ehυ/kT = 1 + hυ/kT + (hυ/kT)2 + . . .
≈ 1 + hυ/kT.

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..
. If hυ/kT is small, its higher powers are neglected.
h hc
... ehυ/kT-1 = 
kT k
Substituting in eqn 1:

 
 8h 
Uλdλ =   d
 5  hc  
   kT  
 

 8k 
=  4  d
  
This is Rayleigh Jeans Law of Radiation.
Compton Effect:

The scattering of a photon by an electron is called as Compton effect or

Compton scattering.

When a photon of wavelength „λ‟ is scattered by an electron in the direction

making an angle „θ‟ with the direction of incidence, the wavelength of the scattered
photon increases. Its wavelength is λ'. The electron recoils in a direction making an
angle „υ ‟ with the incident direction of photon. The difference in the wavelength (λ'-
λ) is called the Compton shift. Compton found that λ' is independent of the target
material, but depends on the angle of scattering.

If λ is the wavelength of the incident photon, its energy E is given by E=hc/λ

where „h‟ is the Planck‟s constant, „c‟ is the velocity of light, „λ‟ is the wavelength of
the incident photon. If λ' is the wavelength of the scattered photon, its energy E' is
given by

E' = hc/λ'

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The energy of the scattered photon is reduced from E to E'. The difference of
energy is carried by recoiling electron at an angle „υ‟ with the incident direction of
photon.

Applying the laws of conservation of energy and conservation of momentum

Compton obtained an expression for change in wavelength  λ given by  λ = λ' – λ
h
= (1  cos  )Where „m‟ is the mass of the electron, h/mc is called as Compton
mc
wavelength. Compton Effect explains particle nature of light.

Dual nature of matter (de-Broglie Hypothesis)

Light exhibits the phenomenon of interference, diffraction, photoelectric effect

and Compton Effect. The phenomenon of interference, diffraction can only be
explained with the concept that light travels in the form of waves. The phenomenon of
photoelectric effect and Compton Effect can only be explained with the concept of
Quantum theory of light. It means to say that light possess particle nature. Hence it is
concluded that light exhibits dual nature namely wave nature as well as particle
nature.

de-Broglie’s Wavelength:

A particle of mass „m‟ moving with velocity „c‟possess energy given by

E = mc2 → (Einstein‟s Equation) (1)

According to Planck‟s quantum theory the energy of quantum of frequency

it

„υ‟is

E = hυ → (2)

From (1) & (2)

mc2 = hυ= hc /λsince υ = c/λ

λ= hc /mc2 = h/mc

λ= h/mv since v ≈ c

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Relation between de-Broglie wavelength and kinetic energy

Consider an electron in an electric potential V, the energy acquired is given by

1 p2
E  eV  mv 2 
2 2m

Where „m‟ is the mass, „v‟ is the velocity and „p‟ is the momentum of the particle. „e‟
is charge of an electron.

p  2meV  2mE

The expression for de-Broglie wavelength is given by

h h h h
   
p mv 2meV 2mE

de-Broglie Wavelength of an Accelerated Electron:

An electron accelerated with potential difference „V‟ has energy „eV‟.If „m‟ is
t
the mass and „v‟ is the velocity of the electron.

Then eV = 1/2(mv2) → (1)

If „p‟ is the momentum of the electron, then p=mv

Squaring on both sides, we have

p2 = m2v2

mv2 = p2/m

Using in equation (1) we have

eV = p2/(2m) or p = (2meV)

According to de-Broglie λ = h/p

Therefore λ=  h = 1  h 

 2meV 
 V 
 2me 


λ= 1  6.626  10 34 
V 

19 
2  9.11  10  1.602  10 
31

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= 1.226  10 λ = 1.226 nm
9
m or
V V

Characteristics of matter waves:

1. Waves associated with moving particles are called matter waves. The wavelength
„λ‟ of a de-Broglie wave associated with particle of mass „m‟ moving with
velocity 'v' is
λ = h/(mv)

2. Matter waves are not electromagnetic waves because the de Broglie wavelength is
independent of charge of the moving particle.
3. The velocity of matter waves (vP) is not constant. The wavelength is inversely

u
proportional to the velocity of the moving particle.
4. Lighter the particle, longer will be the wavelength of the matter waves, velocity
being constant.
5. For a particle at rest the wavelength associated with it becomes infinite. This
shows that only moving particle produces the matter waves.
Phase velocity and group velocity:

A wave is represented by the equation:

y = Asin(ωt-kx)

Where „y‟ is the displacement along Y-axis at an instant t, „ω‟ is the angular
frequency, „k‟ is propagation constant or wave number. „x‟ is the displacement along
x-axis at the instant „t‟.

If „p‟ is the point on a progressive wave, then it is the representative point for a
particular phase of the wave, the velocity with which it is propagated owing to the
motion of the wave is called phase velocity.

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The phase velocity of a wave is given by vphase = (ω /k).

Group velocity:

Individual Waves Amplitude variation after

Superposition

A group of two or more waves, slightly differing in wavelengths are super

imposed on each other. The resultant wave is a packet or wave group. The velocity
with which the envelope enclosing a wave group is transported is called Group
Velocity.

Let y1 = Asin(ωt-kx) → (1) and

r
y2 = Asin[(ω+Δ ω)t - (k+Δk)x] → (2)

The two waves having same amplitude & slightly different wavelength. Where
y1 & y2 are the displacements at any instant„t‟, „A‟ is common amplitude, „ω‟ &
„Δk‟ are difference in angular velocity and wave number are assumed to be small. „x‟
is the common displacement at time „t‟

By the principle of superposition

y = y1 + y2

y = Asin(ωt-kx) + A sin{(ω+Δ ω)t - (k+Δk)x}

a b  a b
But, sin a + sin b = 2 cos  sin 
 2   2 

    k    2     2k  k  
y = 2A cos  t    x sin  t    x
 2   2    2   2  

Since Δω and Δk are small

2ω +Δω ≈ 2ω and 2k + Δk ≈ 2k.

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    k  
... y = 2A cos  t    x sin t  kx → (3)
 2   2  

From equations (1) & (3) it is seen the amplitude becomes

    k  
2A cos  t    x 
 2   2  

The velocity with which the variation in amplitude is transmitted in the

o
resultant wave is the group velocity.

( 
vgroup= 
(k k

 d
In the limit 
k dk

d
vgroup =
dk

Relation between group velocity and phase velocity:

The equations for group velocity and phase velocity are:

d 
vgroup = → (1) &vphase= → (2)
dk k

Where „ω‟ is the angular frequency of the wave and „k‟ is the wave number.

ω = k vphase

d d
vgroup= = (kv phase )
dk dk

dv phase
vgroup= vphase+ k
dk

 dv phase  d 
vgroup = vphase+ k    → (3)
 d   dk 

We have k = (2π/λ)

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dk 2 d 2
Differentiating   2 or 
d  dk 2

d  2  2 
k       
dk    2 

Using this in eqn (3)

dv phase
vgroup = vphase - λ
d

This is the relation between group velocity and phase velocity.

Relation between group velocity and particle velocity:

The equation for group velocity is

d
vgroup = → (1)
dk

But ω=2πυ = 2π(E/h) → (2)

2
d  dE → (3)
h

We have k = 2π/λ = 2π(p/h) → (4)

2
dk  dP → (5)
h
t

Dividing eqn (3) by (5) we have

d dE
 → (6)
dk dP

But we have E = P2/(2m), Where „P‟ is the momentum of the particle.

dE 2 P P
 
dP 2m m

Using the above in eqn (6)

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d P

dk m

But p = mvparticle, Where „vparticle‟ is the velocity of the particle.

d mv particle
  v particle → (7)
dk m

From eqn (1) & (7), we have

vgroup= vparticle → (8)

... The de Broglie‟s wave group associated with a particle travels with a velocity equal
to the velocity of the particle itself.

Relation between velocity of light, group velocity and phase velocity:

We have vphase = ω/k

r
Using the values of „ω‟ and „k‟ from eqn (2) & (4) we have

E mc 2 c2
v phase    → (9)
P mv particle v particle

From eqn (8) vgroup= vparticle

... vphase× vgroup = c2

This is the relation of velocity of light with phase velocity & group velocity.

Since vgroup is same as vparticle& the velocity of material particle can never be
greater than or even equal to c, which shows that phase velocity is always greater
than c.

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Introduction: Classical Mechanics - Quantum Mechanics

Mechanics is the branch of Physics which deals with the study of motion of
objects. The study of motion of objects started from 14th Century. Leonardo da
Vinci, Galileo and Blaisepascal were the beginners. Their study did not have any
logical connection to each other. In the 17th Century Newton consolidated the ideas
of previous workers in addition to his own. He gave a unified theory which accounted
for all types of motions of bodies on common grounds. His work “Principia
mathematica” was published in the year 1687. Newton‟s three laws of motion were
included in his work. 1687 year was recognized as the birth of Mechanics. These
laws were important in the wider fields of study in Physics. For example

p
electrodynamics by Maxwel. By the end of 19th Century in the mind of scientific
community it was that the knowledge of mechanics is complete and only refinement
of the known is required.

In the last part of 19th Century the study of Blackbody radiation became an
insoluble puzzle. It was much against the confidence and belief of many
investigators. Newtonian mechanics failed to account the observed spectrum.In
December 1900 Max Planck explained the blackbody spectrum by introducing the
idea of quanta. This is the origin of “Quantum Mechanics”. Whatever studies were
made in mechanics till then was called classical mechanics. From 1901 onwards
quantum mechanics has been employed to study mechanics of atomic and subatomic
particles. The concept of quantization of energy is used in Bohr‟s theory of hydrogen
spectrum. In 1924 de-Broglie proposed dual nature of matter called de Broglie
hypothesis. Schrodinger made use in his work the concepts of wave nature of matter
and quantization of energy. The work of Schrodinger, Heisenberg, Dirac and others
on mechanics of atomic and subatomic particles was called Quantum Mechanics.

Difference between Classical Mechanics and Quantum Mechanics

According to Classical mechanics it is unconditionally accepted that the

position, mass, velocity, acceleration etc., of a particle or a body can be measured
accurately, which is true as we observe in every day. The values predicted by
classical mechanics fully agree with measured values.

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Quantum mechanics has been built upon with purely probabilistic in nature. The
fundamental assumption of Quantum mechanics is that it is impossible to measure
simultaneously the position and momentum of a particle. In quantum mechanics the
measurements are purely probable. For example the radius of the first allowed orbit
of electron in hydrogen atom is precisely 5.3 x 10 -11 m. If a suitable experiment is
conducted to measure the radius, number of values are obtained which are very close
to 5.3 x 10-11m. This type of uncertainty makes classical mechanics superior to
quantum mechanics. The accurate values declared by classical mechanics are found
to be true in day to day life. But in the domain of nucleus, atoms, molecules etc., the
probabilities involved in the values of various physical quantities become
insignificant and classical mechanics fails to account such problems.
Heisenberg‟s Uncertainty Principle:
According to classical mechanics a particle occupies a definite place in space
and possesses a definite momentum. If the position and momentum of a particle is
known at any instant of time, it is possible to calculate its position and momentum at
any later instant of time. The path of the particle could be traced. This concept breaks
down in quantum mechanics leading to Heisenberg‟s Uncertainty Principle according
to which “It is impossible to measure simultaneously both the position and
momentum of a particle accurately. If we make an effort to measure very accurately
the position of a particle, it leads to large uncertainty in the measurement of
momentum and vice versa.
If ∆ x and Px are the uncertainties in the measurement of position and
momentum of the particle then the uncertainty can be written as

∆ x . Px ≥ (h/4π)
.

In any simultaneous determination of the position and momentum of the

particle, the product of the corresponding uncertainties inherently present in the
measurement is equal to or greater than h/4π.

Similarly, 1) ∆E.∆t ≥ h/4π This equation represents uncertainty in energy and

time. ∆E is uncertainty in energy,∆t is the uncertainty in time.

2) ∆L.∆θ ≥ h/4π This equation represents uncertainty in angular

momentum(∆L) and angular displacement(∆θ)

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Application of Uncertainty Principle:

Impossibility of existence of electrons in the atomic nucleus:

According to the theory of relativity, the energy E of a particle is: E = mc² =

mo c 2
1  v 2 / c 2 

Where „mo‟ is the rest mass of the particle and „m‟ is the mass when its velocity is „v‟.

.
mo2 c 4 mo2 c 6
i.e. E 
2
= → (1)
1  v 2 / c 2  c 2  v 2

If „p‟ is the momentum of the particle:

mo v
i.e. p = mv =

1  v2 / c2 
mo2 v 2 c 2
p² = 2
c  v2

Multiply by c²

mo2 v 2 c 4
p²c² = 2 → (2)
c  v2

Subtracting (2) by (1) we have

mo2 c 4 (c 2  v 2 )
E² - p²c² =
c2  v2

E² = p²c² + mo2c4 → (3)

Heisenberg‟s uncertainty principle states that

h
∆ x . Px ≥ → (4)
4

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The diameter of the nucleus is of the order 10-14 m. If an electron is to exist

inside the nucleus, the uncertainty in its position ∆ x must not exceed 10-14 m.

i.e. ∆ x ≤ 10-14m

The minimum uncertainty in the momentum

6.63  1034
Px min ≥ h
≥ ≥ 0.5 × 10-20 kg.m/s → (5)
4 x max 4  10 14

By considering minimum uncertainty in the momentum of the electron

i.e., Px min ≥ 0.5 × 10-20 kg.m/s = p → (6)

Consider eqn (3)

E² = p²c² + mo2c4 = c2(p²+mo²c²)

Where mo= 9.11 × 10-31 kg

If the electron exists in the nucleus its energy must be

n

E² ≥ (3 × 108)2[(0.5 × 10-20)2 + (9.11 × 10-31)2(3 × 108)2]

i.e. E² ≥ (3 × 108)2[0.25 × 10-40 + 7.4629 × 10-44]

Neglecting the second term as it is smaller by more than the 3 orders of the
magnitude compared to first term.

Taking square roots on both sides and simplifying

1.5  10 12
E ≥ 1.5 × 10-12 J ≥ ev ≥ 9.4 Mev
1.6  10 19

If an electron exists in the nucleus its energy must be greater than or equal to
9.4Mev. It is experimentally measured that the beta particles ejected from the nucleus
during beta decay have energies of about 3 to 4 MeV. This shows that electrons
cannot exist in the nucleus.

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Wave Function:

A physical situation in quantum mechanics is represented by a function called

wave function. It is denoted by „ψ‟. It accounts for the wave like properties of
particles. Wave function is obtained by solving Schrodinger equation. To solve
Schrodinger equation it is required to know

1) Potential energy of the particle

2) Initial conditions and

3) Boundary conditions.

There are two types of Schrodinger equations:

1) The time dependent Schrodinger equation: It takes care of both the position and
time variations of the wave function. It involves imaginary quantity i.

d 2
h2 ih d
The equation is:  2  V  
8 m dx 2
2 dt

2) The time independent Schrodinger equation: It takes care of only position

e

variation of the wave function.

d 2 8 2 m
The equation is:  2 ( E  V )  0
dx 2 h

Time independent Schrodinger wave equation

Consider a particle of mass „m‟ moving with velocity „v‟. The de-Broglie
wavelength „λ‟ is

h h
λ=  → (1)
mv P

Where „mv‟ is the momentum of the particle.

The wave eqn is

  A ei ( kx  t ) → (2)
Where „A‟ is a constant and „ω‟ is the angular frequency of the wave.

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Differentiating equation (2) with respect to „t‟ twice

d 2
  A 2 e i ( kx t )   2 → (3)
dt 2

The equation of a travelling wave is

d2y 1 d2y

dx 2 v 2 dt 2

Where „y‟ is the displacement and „v‟ is the velocity.

Similarly for the de-Broglie wave associated with the particle

d 2 1 d 2
 → (4)
dx 2 v 2 dt 2

where „ψ‟ is the displacement at time „t‟.

From eqns (3) & (4)

d 2 2
 2
dx 2 v

But ω = 2πυ and v =υ λ where „υ‟ is the frequency and „λ‟ is the wavelength.
t

d 2 4 2 1 1 d 2
  2  or 2   2 → (5)
dx 2   4  dx 2

1 2 m2 v2 P 2
K .E  mv   → (6)
2 2m 2m

h2
 → (7)
2m2

Using eqn (5)

h2  1  d 2 h 2 d 2
K .E     2 → (8)
2m  4 2  dx 2 8 m dx 2

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Total Energy E = K.E + P.E

h 2 d 2
E 2 V
8 m dx 2

h 2 d 2
E V  
8 2 m dx 2

d 2 8 2 m
  E  V 
dx 2 h2

d 2 8 2 m
 E  V   0
dx 2 h2

This is the time independent Schrodinger wave equation.

Physical significance of wave function:

Probability density:If ψ is the wave function associated with a particle, then |ψ|² is the
probability of finding a particle in unit volume. If „τ‟ is the volume in which the
particle is present but where it is exactly present is not known. Then the probability of
e

finding a particle in certain elemental volume dτ is given by |ψ| 2dτ. Thus |ψ|² is called
probability density. The probability of finding an event is real and positive quantity.
In the case of complex wave functions, the probability density is |ψ|² = ψ * ψ where
ψ* is Complex conjugate of .

Normalization:

The probability of finding a particle having wave function „ψ‟ in a volume „dτ‟
is „|ψ|²dτ‟. If it is certain that the particle is present in finite volume „τ‟, then

 | | ² d  1
0

If we are not certain that the particle is present in finite volume, then


 | | ²d  1


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In some cases  | | ²d  1 and involves constant.

The process of integrating the square of the wave function within a suitable limits and
equating it to unity the value of the constant involved in the wavefunction is
estimated. The constant value is substituted in the wavefunction. This process is
called as normalization. The wavefunction with constant value included is called as
the normalized wavefunction and the value of constant is called normalization factor.

Properties of the wave function:

A system or state of the particle is defined by its energy, momentum, position

etc. If the wave function „ψ‟ of the system is known, the system can be defined. The
wave function „ψ‟ of the system changes with its state.
To find „ψ‟ Schrodinger equation has to be solved. As it
is a second order differential equation, there are several
solutions. All the solutions may not be correct. We have
to select those wave functions which are suitable to the
system. The acceptable wave function has to possess the
following properties:

1) „ψ‟ is single valued everywhere: Consider the function f( x ) which varies with
u

position as represented in the graph. The function f(x) has three values f1, f2 and f3 at
x = p. Since f1 ≠ f2≠ f3 it is to state that if f( x ) were to be the wave function. The
probability of finding the particle has three different values at the same location which
is not true. Thus the wave function is not acceptable.

2) „ψ‟ is finite everywhere: Consider the function f( x ) which varies with position
as represented in the graph. The function f( x ) is not finite at x =R but f( x )=∞.

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Thus it indicates large probability of finding the particle at a location. It violates

uncertainty principle. Thus the wave function is not acceptable.

3) „ψ‟ and its first derivatives with respect to its variables are continuous
everywhere: Consider the function f( x ) which varies with position as represented in

.
the graph. The function f( x ) is truncated at x =Q between the points A & B, the
state of the system is not defined. To obtain the wave function associated with the
system, we have to solve Schrodinger wave equation. Since it is a second order
differential wave equation, the wave function and its first derivative must be
continuous at x=Q. As it is a discontinuous wave function, the wave function is not
acceptable.

4) For bound states „ψ‟ must vanish at potential boundary and outside. If „ψ*‟ is a
complex function, then ψ* ψ must also vanish at potential boundary and outside.

The wave function which satisfies the above 4 properties are called Eigen
functions.

Eigen functions:

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Eigen functions are those wave functions in Quantum mechanics which

possesses the properties:

1. They are single valued.

2. Finite everywhere and
3. The wave functions and their first derivatives with respect to their variables are
continuous.
Eigen values:

According to the Schrodinger equation there is more number of solutions. The

wave functions are related to energy E. The values of energy E n for which

p
Schrodinger equation solved are called Eigen values.

Application of Schrodinger wave equation:

Energy Eigen values of a particle in one dimensional, infinite potential well (potential
well of infinite depth) or of a particle in a box.

Y-Axis

V= V=0 V=

Particle x=0 xx=a X-Axis

Consider a particle of a mass „m‟ free to move in one dimension along positive
x -direction between x =0 to x =a. The potential energy outside this region is
infinite and within the region is zero. The particle is in bound state. Such a
configuration of potential in space is called infinite potential well. It is also called
particle in a box. The Schrödinger equation outside the well is

d 2 8 2 m
 E    0 → (1) ∵V = ∞
dx 2 h2

For outside, the equation holds good if ψ = 0 & |ψ|² = 0. That is particle cannot be
found outside the well and also at the walls

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The Schrodinger‟s equation inside the well is:

d 2 8 2 m
 E  0 → (2) ∵V = 0
dx 2 h2

h2 d 2
  E → (3)
8 2 m dx 2

This is in the form Ĥψ = Eψ

This is an Eigen-value equation.

8 2 m
Let 2
E  k 2 in eqn (2)
h

d 2
2
 k 2  0
dx

The solution of this equation is:

ψ = C cos k x + D sin k x → (4)

n

at x = 0 → ψ = 0

0 = C cos 0 + D sin 0

∴C=0

Also x=a→ψ=0
0 = C coska + D sin ka

But C = 0

∴D sin ka = 0 (5)

D0 (because the wave concept vanishes)

i.e. ka = nπ where n = 0, 1, 2, 3, 4… (Quantum number)

n
k= → (6)
a

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Using this in eqn (4)

n
 n  D sin x → (7)
a

Which gives permitted wave functions.

m
To find out the value of D, normalization of the wave function is to be done.

co
a


2
i.e. n dx  1 → (8)
0

p.
using the values of ψn from eqn (7)

ou
a
n
D
2
sin 2 xdx  1
0
a

D2 
a
1  cos( 2n / a ) x 
D2  
0 
a a
2
2 n
dx  1


gr  1  cos 2 
 sin 2   
 2


ts
  dx   cos xdx   1
2 0 0
a 
en

a
D2  a 2 n 
2  x  2n sin a x   1
0

D2
a  0  1
ud

2
D2
a 1
2
st

2
D
a
ity

Hence the normalized wave functions of a particle in one dimensional infinite

potential well is:
.c
w

2 n
n  sin x → (9)
a a
w

Energy Eigen values:

w

From Eq. 6 &2

8 2 m 2 n 2 2
E  k 
h2 a2
n2h2
E
8ma2

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Implies

Alternative Method (Operator method)

Energy Eigen values are obtained by operating the wave function „ψ‟ by the energy
operator (Hamiltonian operator).

h2 d2
Ĥ=  V
8 2 m dx 2

Inside the well 0 < x < a, V=0

h2 d2
Ĥ=  → (10)
8 2 m dx 2

The energy Eigen value eqn is

Ĥψ=Eψ→(11)

From equation (10) and (11)

d 2 n
h2
 2  E
8 m dx 2

h 2 d 2 n
i.e.  2  E n → (12)
8 m dx 2
t

It is the Eigen value equation.

Differentiating eqn (9)

d n 2 n n
 cos x
dx a a a

Differentiating again

2
d 2 n 2  n  n
   sin x
dx 2
a a  a

2
d 2 n  n 
   n
 a 
2
dx

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Using this eqn. in (12)

2
h 2  n 
   n  E n
8 2 m  a 

n2h2
E= → (13)
8ma 2

It gives the energy Eigen values of the particle in an infinite potential well.

n = 0 is not acceptable inside the well because ψ n = 0. It means that the electron
is not present inside the well which is not true. Thus the lowest energy value for n = 1

p
is called zero point energy value or ground state energy.

h2
i.e. Ezero-point =
8ma 2

The states for which n >1 are called exited states.

Wave functions, probability densities and energy levels for particle in an infinite
potential well:

Let us consider the most probable location of the particle in the well and its
energies for first three cases.

Case I → n=1

It is the ground state and the particle is normally present in this state.

The Eigen function is

2 
ψ1= Sin x ∵from eqn (7)
a a

ψ1 = 0 for x = 0 and x = a
But ψ1 is maximum when x = a/2.

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1 1
2

x=0 a/2 x=a x=0 a/2 x=a

The plots of ψ1 versus x and | ψ1|2 verses x are shown in the above figure.

|ψ1|2 = 0 for x = 0 and x = a and it is maximum for x = a/2. i.e. in ground state the

c
particle cannot be found at the walls, but the probability of finding it is maximum in
the middle.

The energy of the particle at the ground state is

h2
E1 = = E0
8ma 2

Case II → n=2

In the first excited state the Eigen function of this state is

2 2
ψ2 = Sin x
a a

ψ2= 0 for the values x = 0, a/2, a.

Also ψ2 is maximum for the values x = a/4 and 3a/4.

These are represented in the graphs.

| ψ2|2 = 0 at x = 0, a/2, a, i.e. particle cannot be found either at the walls or at the

2 a 3a
centre.  2  maximum for x  , x 
4 4

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ψ2 | ψ2|2
a/4 3a/4
a/4
3a/4
x=0 a/2 x=0 a/2 x=a
x=a

The energy of the particle in the first excited state is E 2 = 4E0.

Case III → n=3

In the second excited state,

2 3
ψ3= Sin x
a a

ψ3 = 0, for x = 0, a/3, 2a/3 and a.

ψ3 is maximum for x = a/6, a/2, 5a/6.

These are represented in the graphs.

a a 5a
x = 0, a/3, 2a/3 and a.  3  maximum for x  , x  , x 
2
| ψ3 |2 = 0 for
6 2 6
c

The energy of the particle in the second excited state is E 3=9 E0.

Energy Eigen values of a free particle:

A free particle is one which has zero potential. It is not under the influence of
any force or field i.e. V = 0.

The Schrodinger equation is:

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d 2 8 2 m
 E  0
dx 2 h2

h2 d 2
or   E
8 2 m dx 2

This equation holds good for free particle in free space in which V = 0.

With the knowledge of the particle in a box or a particle in an infinite potential

well V = 0 holds good over a finite width „a‟ and outside V = ∞. By taking the width
to be infinite i.e. a = ∞, the case is extended to free particle in space. The energy
Eigen values for a particle in an infinite potential well is

.
n2h2
E=
8ma 2

Where n =1, 2, 3, …

2a
n 2mE
h

Here when „E‟ is constant, „n‟ depends on „a‟ as a→∞ n→∞. It means that free
particle can have any energy. That is the energy Eigen values or possible energy
values are infinite in number. It follows that energy values are continuous. It means
that there is no discreteness or quantization of energy. Thus a free particle is a
„Classical entity‟.

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