UNIT I – QUANTUM MECHANICS

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Content:

de Broglie Hypothesis and Matter Waves, de Broglie wavelength and

derivation of expression by analogy, Phase Velocity and Group
Velocity, Heisenberg’s Uncertainty Principle and its application.
Wave Mechanics:Wave function, Time independent Schrodinger wave
equation, Physical Significance of a wave function, Expectation value,
Eigen functions and Eigen Values, Motion of a particle in a one-
dimensional potential well of infinite depth, Wave function and
Probabilities. Numerical problems.

Introduction:
At the beginning of the 20th century, Newton’s laws of
motion were able to successfully describe the motion of the
particles in classical mechanics (the world of large, heavy and slow
bodies) and Maxwell’s equations explained phenomena in classical
electromagnetism. However the classical theory does not hold in
the region of atomic dimensions. It could not explain the stability
of atoms, energy distribution in the black body radiation spectrum,
origin of discrete spectra of atoms, etc. It also fails to explain the
large number of observed phenomena like photoelectric effect,
Compton Effect, Raman Effect, Quantum Hall effect,
superconductivity etc. The insufficiency of classical mechanics
led to the development of quantum mechanics (QM).

Quantum mechanics gives the description of motion and

interaction of particles in the small scale atomic system where the
discrete nature of the physical world becomes important. With the
application of quantum mechanics, most of the outstanding
problems have been solved. The direct implications of QM though
very subtle have dramatic effect in our day to day life. For

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example, QM successfully introduced the concept of discrete

energy which led to the conception and advancements in quantum
computing, it also paved way for efficient long distance transfer of
large quantities of data electronically. By understanding the
electronic spin and related atomic properties, QM has aided in
realizing energy efficient materials that can be applied to
consumable electronic equipment and in commercial transport
vehicles like Hyper loop, Maglev trains among others.

Black Body Radiation

Black-body radiation is the type of electromagnetic
radiation emitted by a black body (an opaque and non-reflective
body) held at constant, uniform temperature. In nature there are no
perfect black bodies.
Black Body Spectrum: It is a graph showing the variation of
the energy of the black body radiations as a function of their
wavelengths or frequencies.The energy distribution in the black
body spectrum is explained by Wien’s distribution law in the
lower wavelength region and Rayleigh Jean’s law explains the
energy distribution in the larger wavelength region.
Wien’s law:
B
E d  A e 5 T
d

Rayleigh Jeans law:

E d  8k T4 d

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Fig: Blackbody Radiation spectrum

Neither Wien’s law nor Rayleigh- jean’s law could explain
the energy distribution in the entire blackbody spectrum. The
energy distribution in the entire blackbody spectrum was
successfully explained by Max. Planck’s quantum Theory.

Planck’s quantum theory

The energy distribution in the black body radiation spectrum
was successfully explained by Max Planck in the year 1900.
According to Planck’s quantum theory thermal energy is not
emitted or absorbed continuously, but it is emitted or absorbed in
discrete quantities called quanta. Each quanta has an energy ‘hν’
where h is the Planck’s constant. Applying the Planck’s quantum
theory an expression for the energy distribution in the black body
spectrum was obtained and it is called Planck’s formula.

The Planck’s formula is as follows

8hc 1
E d  d
 5
e
( hc
kT )
1

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Where k is the Boltzmann’s constant; h- Planck’s constant and c is

the velocity of light, λ is the wavelength of the black-body
radiation and ω is the angular frequency of light.

Photoelectric effect:
When the light of a suitable wavelength shines on certain
materials, then electrons are spontaneously emitted from the
surface of material. It can be observed in any material but most
readily in metals and good conductors. This phenomenon is known
as the photoelectric effect.
The materials that exhibit photoelectric effect are called
photosensitive materials and the emitted electrons are called
photoelectrons. Heinrich Hertz first observed this phenomenon in
1887.
The electrons are emitted only when the photons reach or
exceed a threshold frequency (energy) and below that threshold, no
electrons are emitted from the metal regardless of the light
intensity or the length of time of exposure to the light. To explain
this phenomenon, Albert Einstein proposed that light be seen as a
collection of discrete bundles of energy (photons), each with
energy hυ, where υ is the frequency of the light that is being
quantized and h is known as the Planck constant.

Einstein’s photoelectric equation:

Einstein, in 1905, proposed that the light energy is localized in
small packets similar to the Planck’s idea of quanta, and named
such packets as photons. According to Einstein, in photoelectric
effect one photon is completely absorbed by one electron, which
thereby gains the quantum of energy and may be emitted from the
metal.

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Thus the photon energy is used in the following two parts:

i). A part of its energy is used to free the electron from the
atoms of the metal surface. This energy is known as a photoelectric
work function of metal (Wo)
ii) The other part is used in giving kinetic energy (½ mv2) to
the electron.
1
Thus h  Wo  mv 2 Where ‘v’ - velocity of the emitted electron.
2
This equation is known as Einstein’s photoelectric equation.

When the photon’s energy is of such a value that it can just

liberate the electron from metal, then the kinetic energy of the
electron will be zero. Then the above equation reduces to h o  Wo
, where  o is called the threshold frequency.
Threshold frequency is defined as the minimum frequency which
can cause photoelectric emission. Below this frequency no
emission of electron takes place.

Compton Effect:
When a monochromatic beam of high frequency radiation (X –
rays, γ – rays, etc.) is scattered by a substance, then the scattered
radiation contains two components - one having a lower frequency
or greater wavelength called as modified radiation and the other
having the same frequency or wavelength called as unmodified
radiation. This phenomenon is known as Compton Effect and was
discovered by Prof. A.H. Compton in 1921. The process of
recoiling of electron and scattering of photon is as shown in the
following figure:

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Scattered photon

Electron
Incident photon at rest
θ
φ
Recoil electron
Φ----- is the recoil angle
θ------ is the scattering angle.

Fig: Schematic diagram of Compton Effect

According to the quantum concept of radiation, the radiation

is constituted by energy packets called photons. The energy of
photon is hν, where h is Planck’s constant and ν is the frequency of
radiation. The photons move with velocity of light c, possess
momentum hν/c and obey all the laws of conservation of energy
and momentum. According to Compton, the phenomenon of
scattering is due to an elastic collision between two particles, the
photon of incident radiation and the electron of the scatterer. When
the photon of energy hν collides with the electron of the scatterer at
rest, it transfers some energy to the electron, i.e., it loses the
energy. The scattered photon will therefore have a smaller energy
and consequently a lower frequency (ν’) or greater wavelength(λ’)
than that of the incident photon. The observed change in frequency
or wavelength of the scattered radiation is known as Compton
Effect. In the scattering process, the electron gains kinetic energy
and thus recoils with a velocity v. The changed wavelength of the
photon scattered through an angle θ is given by

h
  (  '   )  [1  cos ]
m0 c

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Wave and particle duality of radiation

To understand the wave and particle duality, it is necessary to
know what a particle is and what a wave is.
A particle is a localized mass and it is specified by its mass,
velocity, momentum, energy, etc. In contrast a wave is a spread
out disturbance. A wave is characterized by its wavelength,
frequency, velocity, amplitude, intensity, etc. It is hard to think
mass being associated with a wave. Considering the above facts, it
appears difficult to accept the conflicting ideas that radiation has a
wave particle duality. However this acceptance is essential because
the radiation exhibits phenomena like interference, diffraction,
polarization, etc., and shows the wave nature and it also exhibits
the particle nature in the black-body radiation effect, photoelectric
effect, Compton Effect etc.
Radiation, thus, sometimes behave as a wave and at some other
time as a particle, this is the wave particle duality of radiation.

De Broglie’s concept of matter waves.

Louis de-Broglie in 1924 extended the wave particle dualism
of radiation to fundamental entities, such as electrons, protons,
neutrons, atoms, molecules, etc. de-Broglie put a bold suggestion
that like radiation, matter also has dual characteristic, at a time
when there was absolutely no experimental evidence for wave like
properties of matter waves. de-Broglie Hypothesis of matter
waves is as follows.
 In nature energy manifests itself in two forms, namely matter
and radiation.
 Nature loves symmetry.

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 As radiation can act like both wave and a particle, material

particles (like electrons, protons, etc.) in motion should exhibit
the property of waves.
These waves due to moving matter are called matter waves or de-
Broglie waves or pilot waves.

Wavelength of matter waves:

The concept of matter waves is well understood by combining
Planck’s quantum theory and Einstein’s theory. Consider a photon
of energy E, frequency γ and wavelength λ.
hc
By Planck’s theory E  h 

By Einstein’s mass-energy relation E  mc 2
By equating and rearranging the above equations, we get
hc
mc 2 

h h
 
mc p
Where, p is the momentum of the photon and h is a Planck’s
constant.
Now consider a particle of mass m moving with a velocity v
and momentum p. According to the de-Broglie hypothesis matter
also has a dual nature. Hence the wavelength λ of matter waves is
given by
h h
 
mv p
This is the equation for the de-Broglie wavelength.

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De Broglie wavelength of an electron

Consider an electron of mass ‘m’ accelerated from rest by an
electric potential V. The electrical work done (eV) is equal to the
kinetic energy E gained by the electron.
E  eV
1
 E  mv 2
2
 m v  2mE
2 2

mv  2mE

Therefore wavelength of electron wave

h h
 
p mv
h
 
2mE
But E  eV
h
h 2me
  
2meV V
Substituting the values of e, m and h, we get
h
 12.28 Ao
2me
12.28 o
  A
V
Note: Instead of a an electron, if a particle of charge ‘q’ is
accelerated through a potential difference V, then
h

2mqV

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Properties of matter waves and how they are different from

electromagnetic waves

1. Lighter the particle, greater would be the wavelength of

matter waves associated with it.
2. Smaller the velocity of the particle, greater would be the
wavelength.
3. For p = 0, λ is infinity ie., the wave becomes indeterminate.
This means that matter waves are associated with moving
particles only.
4. Matter waves are produced by charged or uncharged particles
in motion. Whereas electromagnetic waves are produced only
by a moving charged particle. Hence matter waves are non –
electromagnetic waves.
5. In an isotropic medium the wavelength of an electromagnetic
wave is a constant, whereas wavelength of a matter wave
changes with the velocity of the particle. Hence matter waves
are non- electromagnetic waves.
6. A particle is a localized mass and a wave is a spread out
disturbance. So, the wave nature of matter introduces a
certain uncertainty in the position of the particle.
7. Matter waves are probability waves because waves represent
the probability of finding a particle in space.

Wave Packet
A wave packet refers to the case where two (or more) waves
exist simultaneously. A wave packet is often referred to a wave
group. This situation is permitted by the principle of superposition.
In physics, a wave packet (or wave train) is a short "burst" or
"envelope" of localized wave action that travels as a unit. A wave

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packet can be analyzed into, or can be synthesized from, an infinite

set of component sinusoidal waves of different wavenumbers, with
phases and amplitudes such that they interfere constructively only
over a small region of space, and destructively elsewhere. Each
component wave function, and hence the wave packet, are
solutions of a wave equation. Depending on the wave equation, the
wave packet's profile may remain constant (no dispersion) or it
may change (dispersion) while propagating.

Phase velocity and Group velocity

A monochromatic wave has velocity called the phase velocity

given by v p    where ω is the angular frequency, k  2 is
k 
the wave number, υ is the frequency.
However, if we have a compound wave(wave packet) that is
composed of individual waves with a range of frequencies, each
individual wave has its phase velocity, but the amplitudes of the
waves add up to produce a wave packet which has a velocity all its
own. This velocity is called the group velocity (vg) and is usually
different from the individual phase velocities of the waves that
make up the wave packet. Such a wave packet possesses both wave
and particle properties. Schrodinger postulated that moving particle
(electron, proton..etc) is equivalent to a wavepacket rather than a
single wave. The velocity with which the resultant envelope of the
group waves travels is called group velocity (vg) and is equal to the
particle velocity (v).
It is given by the expression
 dω
vg   v
k dk

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Fig: Schematic diagram of Wave Packet

Quantum mechanics ascribes a special significance to the wave

packet; it is interpreted as probability amplitude. The modulus
square of the probability amplitude describes the probability
density that a particle in a particular state will be measured to have
a given position or momentum. The equation that describes the
evolution of this wave packet is the Schrödinger equation. It can be
Time independent or Time dependent.

Relation between group velocity and phase velocity

Consider a non-relativistic particle of mass m having vp and vg
as the phase velocity and group velocity respectively. If λ is the de
Broglie Wavelength and ν the frequency of the wave, then


Phase velocity v p 
k
Where ω is the angular frequency of the wave
and k is the wave vector
   v p k

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d  d (v p k )
Group velocity vg  
dk dk
dv p
 vp  k
dk
dv d 
 v p  (k ) p
d  dk
2 2
Where k  or  
 k

d d  2  2
Differentiating,   
dk dk  k  k2

dv p  2 
vg  v p  (k )  
d  k 2 
2  dv p  2
vg  v p     
k  d  k

This equation shows that vg is less than vp, medium is dispersive. For
a light wave in vacuum, there is no dispersion. Hence dvp / dλ = 0,
so that vg = vp=c . This is true for elastic waves in a homogenous
medium.

Heisenberg’s uncertainty principle

Heisenberg’s uncertainty principle is a direct consequence of
the dual nature of matter. In classical mechanics, a moving particle
at any instant has a fixed position in space and a definite
momentum which can be determined if the initial values are known
(we can know the future if we know the present)

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In wave mechanics a moving particle is described in terms of

a wave group or wave packet. According to Max Born’s
probability interpretation the particle may be present anywhere
inside the wave packet. When the wave packet is large, the
momentum can be fixed, but there is a large uncertainty in its
position. On the other hand, if the wave packet is small the position
of the particle may be fixed, but the particle will spread rapidly and
hence the momentum (or velocity) becomes indeterminate. In this
way certainty in momentum involves uncertainty in position and
the certainty in position involves uncertainty in momentum. Hence
it is impossible to know within the wave packet where the particle
is and what is its exact momentum. (We cannot know the future
because we cannot know the present). Thus we have
Heisenberg’s uncertainty principle.

According to the Heisenberg’s uncertainty principle “It is

impossible to specify precisely and simultaneously certain pairs of
physical quantities like position and momentum that describe the
behavior of an atomic system”. Qualitatively, this principle states
that in any simultaneous measurement the product of the
magnitudes of the uncertainties of the pairs of physical quantities is
equal to or greater than h/4π (or of the order of h)

Considering the pair of physical quantities such as position and

momentum, we have
ΔpΔx ≥ h/4π .….1

Where Δp and Δx are the uncertainties in determining the

momentum and the position of the particle.

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Similarly, we have other canonical forms as

ΔEΔt≥ h/4π ……2
ΔJΔθ≥ h/4π ……3
Where ΔE and Δt are uncertainties in determining energy and time
while ΔJ and Δθ are uncertainties in determining angular
momentum and angular position.

Illustration of Heisenberg’s uncertainty principle

Broadening of spectral lines
When an atom absorbs a photon, it rises to the excited state and
it will stay in the excited state for certain time called the lifetime.
Lifetime of atoms in the excited levels is of the order of 10-8s.
When the atom comes to the ground state it emits a photon of
energy exactly equal to the energy difference between the two
levels as shown in the figure.

λ ΔE

Δλ
Intensity

E =hν E =hν

Fig: Line width for emitted photons

The energy of the emitted photon is given by
hc
E  h  .................(1)
 .
Where h is a Planck’s constant, ν is the frequency, c is the
velocity of light and λ is the wavelength.

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Differentiating equation (1) with respect to wavelength (λ), we get

hc
   2

hc
E  .................(2)
2
According to Heisenberg’s uncertainty principle, the finite
lifetime Δt of the excited state means there will be an uncertainty
in the energy of the emitted photon is given by
h
 
4t
Substituting for ΔE from (2) and applying the condition of
minimum uncertainty, we get
hc h

 2
4t

2
or  
4 ct
This shows that for a finite lifetime of the excited state, the
measured value of the emitted photon wavelength will have a
spread of wavelengths around the mean value λ. This uncertainty
in the measured value of wavelength demands for very narrow
spread, the lifetime of the excited state must be very high (of the
order of 10-3s). Such excited levels are called metastable states.
This concept is adopted in the production of laser light.

Principle of Complementarity
One of the milestones of quantum mechanics is Bohr's
complementarity principle. It states that a single quantum can exhibit
a particle-like or a wave-like behavior, but never both at the same
time. These are mutually exclusive and complementary aspects of the

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quantum system. This means that we need distinct experimental

arrangements in order to measure the particle or the wave nature of a
physical system. One of the most known representations of this
principle is the single-photon interferometer. When the interferometer
is closed an interference pattern is observed (wave aspect of the
quantum) while if it is open, the quantum behaves like a particle.

S CHRÖDI NGER ’ S W AVE E QUATION

In1926 Schrödinger starting with de-Broglie equation (λ =
h/mv) developed it into an important mathematical theory called
wave mechanics which found a remarkable success in explaining
the behavior of the atomic system and their interaction with
electromagnetic radiation and other particles. In water waves, the
quantity that varies periodically is the height of water surface. In
sound waves it is pressure. In light waves, electric and magnetic
fields vary. The quantity whose variation gives matter waves is
called wave function (ψ).
The value of wave function associated with a moving body at
a particular point x in space at a time t is related to the likelihood
of finding the body there at a time. A wave function ψ(x,t) that
describes a particle with certain uncertainty in position, moving in
a positive x-direction with precisely known momentum and kinetic
energy may assume any one of the following forms: Sin(ωt -kx) ,
cos( ωt -kx), ei(ωt – kx), e-i(ωt – kx)or some linear combinations of them.

Schrödinger wave equation is the wave equation of which the

wave functions are the solutions. It cannot be derived from any
basic principles, but can be arrived at, by using the de-Broglie
hypothesis in conjunction with the classical wave equation.

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Time Independent one dimensional Schrödinger wave equation

(TISE)
In many situations the potential energy of the particle does not
depend on time explicitly; the force that acts on it, and hence the
potential energy vary with the position of the particle only. The
Schrödinger wave equation for such a particle is time independent
wave equation. Let ψ(x,t) be the wave function of the matter wave
associate with a particle of mass m moving with a velocity v. The
differential equation of the wave motion is as follows.
 2 1  2
 .......... .(1)
x 2 v 2 t 2
The solution of the Eq.(1) as a periodic displacement of time t is
ψ(x,t) =ψ0(x)e-iωt …..(2)
Where ψ0(x) is the amplitude of the matter wave.
Differentiating Eq.2 partially twice w.r.t. to t, we get

 i ψ0(x) e-iωt
t
 2
 i 2 2 ψ0(x) e-iωt
t 2
 2
  2 ψ0(x)e-iωt
t 2
 2
 -  2 ψ ……...(3)
t 2
 2 2
Substituting Eq.3 in Eq.1   2  …(4)
x 2 v
2
2  2  4 2
We have  k  
2
  2

  
2
v 

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Substituting this in Eq4, we get

 2 4 2
   .......... .(5)
x 2 2
 2 4 2
 2   0.......... .(6)
x 2 
Substituting the wavelength of the matter waves λ=h/mv in Eq.6
we get
 2 2 2
2 m v
 4   0.......... .(7)
x 2 h2
If E and V are the total and potential energies of the particle
respectively, then the kinetic energy of the particle
1
E  mv 2  E  V
2
 m 2 v 2  2 m( E  V )
Substituting this in Eq.7, we get
 2 8 2 m
 2 ( E  V )  0.......... .(8)
x 2 h
Hence ψ is a function of x alone and is independent of time. This
equation is called the Schrödinger time- independent one
dimensional wave equation.

Physical significance of the wave function

The wave function ψ(x, t) is the solution of Schrödinger wave
equation. It gives a quantum-mechanically complete description of
the behavior of a moving particle. The wave function ψ cannot be
measured directly by any physical experiment. However, for a
given ψ, knowledge of usual dynamic variables, such as position,

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momentum, angular momentum, etc., of the particle is obtained by

performing suitable mathematical operations on it.

The most important property of ψ is that it gives a measure of

the probability of finding a particle at a particular position. ψ is
also called the probability amplitude. In general ψ is a complex
quantity, whereas the probability must be real and positive.
Therefore a term called probability density is defined. The
probability density P (x,t) is a product of the wave function ψ
and its complex conjugate ψ*.
 P( x, t )   *   ( x, t )
2

The Born interpretation of the wavefunction

The interpretation of the wave function in terms of the location of

the particle is based on a suggestion made by Max Born. He made
use of an analogy with the wave theory of light, in which the
square of the amplitude of an electromagnetic wave in a region is
interpreted as its intensity and therefore (in quantum terms) as a
measure of the probability of finding a photon present in the
region. The Born interpretation of the wavefunction focuses on the
square of the wavefunction (or the square modulus, |ψ|2 = ψ*ψ, if
ψ is complex). It states that the value of |ψ|2 at a point is
proportional to the probability of finding the particle in a region
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around that point. If the wavefunction of a particle has the value ψ

at some point x, then the probability of finding the particle
between x and x + dx is proportional to |ψ|2dx. Thus, |ψ|2 is the
probability density, and to obtain the probability it must be
multiplied by the length of the infinitesimal region dx. The
wavefunction ψ itself is called the probability amplitude. The Born
interpretation does away with any worry about the significance of
a negative (and, in general, complex) value of ψ because |ψ|2 is real
and never negative. There is no direct significance in the negative
(or complex) value of a wavefunction: only the square modulus, a
positive quantity, is directly physically significant, and both
negative and positive regions of a wavefunction may correspond to
a high probability of finding a particle in a region.

Normalization of wave function

If ψ is a wave function associated with a particle, then  2 d
is the probability of finding the particle in a small volume dτ. If it
is certain that the particle is present in a volume τ then the total
probability in the volume τ is unity i.e.,  2 d  1 .This is the


normalization condition.
In one dimension the normalization condition is  2 dx  1
x

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Note: When the particle is bound to a limited region the probability

of finding the particle at infinity is zero i.e., * at x   is zero.

Properties of wave function:

The wave function ψ should satisfy the following properties to
describe the characteristics of matter waves.
1.ψ must be a solution of Schrödinger wave equation.
2.The wave function ψ should be continuous and single valued
everywhere. Because it is related to the probability of finding a
particle at a given position at a given time, which will have only
one value.
3.The first derivative of ψ with respect to x should be continuous
and single valued everywhere, since it is related to the
momentum of the particle which should be finite.
4.Ψ must be normalized so that ψ must go to 0 as x   , so that
 d over all the space be a finite constant.
2

Expectation Values:

To relate a quantum mechanical calculation to something you

can observe in the laboratory, the "expectation value" of the
measurable parameter is calculated. For the position x, the
expectation value is defined as

This integral can be interpreted as the average value of x that

we would expect to obtain from a large number of measurements.
Alternatively it could be viewed as the average value of position for

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a large number of particles which are described by the same

wavefunction. For example, the expectation value of the radius of
the electron in the ground state of the hydrogen atom is the average
value you expect to obtain from making the measurement for a large
number of hydrogen atoms.While the expectation value of a function
of position has the appearance of an average of the function.

Eigen functions and Eigen values

The Schrödinger wave equation is a second order partial
differential equation; it will have many mathematically possible
solutions (ψ). All mathematically possible solutions are not
physically acceptable solutions. The physically acceptable
solutions are called Eigen functions (ψ).

The physically acceptable wave functions ψ has to satisfy the

following conditions:
1. ψ is single valued.
2. ψ and its first derivative with respect to its variable are
continuous everywhere.
3. ψ is finite everywhere.

Once the Eigen functions are known, they can be used in

Schrödinger wave equation to evaluate the physically measurable
quantities like energy, momentum, etc., these values are called
Eigen values.
^ ^
In an operator equation O   where O is an operator for the
physical quantity and ψ is an Eigen function and λ is the Eigen
value. For example :

H   E

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Where H is the total energy (Hamiltonian) operator, ψ is the Eigen

function and E is the total energy in the system. We can have
similar equations for the momentum

P  p 
Where P is the momentum operator and p denotes the momentum
eigen values. Another example would be :

L Z   m 
Where Lz is the z-component of angular momentum operator and
m is the azimuthal quantum number.
Applications of Schrodinger’s wave equation
1. For a Particle in an one-dimensional potential well of infinite
depth (Particle in a box)

Consider a particle of mass ‘m’

moving freely in x- direction in the
region from x=0 to x=a. Outside this
region potential energy ‘V’ is infinity
and within this region V=0.Outside the
box Schrodinger’s wave equation is
 2  8 2 m
 2 E     0.......... ..(1)
x 2 h

This equation holds good only if  =0 for all points outside the
box i.e.,   0 , which means that the particle cannot be found at
2

all outside the box. Inside the box V = 0, hence the Schrodinger’s
equation is given by,

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Discussion of the solution

The solution of the above equation 2 is given by
  A cos kx  B sin kx.......... (4)
Where A & B are constants which depending on the boundary
conditions of the well.
Now apply boundary conditions for this,

Condition: I at x =0,  = 0.
Substituting the condition I in the equation 4, we get A =0 and B  0.
(If B is also zero for all values of x, ψ is zero. This means that the
particle is not present in the well.)
Now the equation 4 can be written as   B sin kx.......... (5)

Condition: II at x =a,  = 0
Substituting the condition II in equation 5 we get
0= B sin(ka)
Since B  0,
sin ka  0  ka  n
n n 2 2
k k2  where, n  1, 2,3...
a a2

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Substitute the value of k2 in equation (3).

8m 2 E n 2 2
 2
h2 a
2 2
n h
E .......... ......( 6)
8ma 2
The equation (6) gives energy values or Eigen value of the
particle in the well. When n=0, n = 0. This means to say that the
electron is not present inside the box, which is not true. Hence the
lowest value of ‘n’ is 1.
 The lowest energy corresponds to ‘n’=1 is called the zero-point
energy or Ground state energy.
h2
E zero  po int 
8ma 2
All the states of n1 are called excited states.

To evaluate B in equation (3), one has to perform normalization of

wave function.

Normalization of wave function:

n
Consider the equation,   B sin kx  Bsin x
a
The integral of the wave function over the entire space in the box
must be equal to unity because there is only one particle within the
box, the probability of finding the particle is 1.
a

 dx  1
2

0
a
n
B 2  sin 2 xdx  1
0 a

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But sin 2  
1
1  cos 2 
2
 2n x 
a
B2
2  1  cos
0
a 
dx  1`

B  2n x 
2a a

 dx   cos dx   1
2 0 0
a 
 2n x  
a
B2  a
 x  2n sin  a    1
2   0
B2  a 
2  a  2n sin 2n  0   1
B 2a
1 B  2
2 a

Thus the normalized wave function of a particle in a one-

dimensional box is given by,
2  n 
n  sin  x where, n=1,2,3……
a  a 

This equation gives the Eigen functions of the particle in the box.
The Eigen functions for n=1,2,3..are as follows.
2  
1  sin  x
a a
2  2 
2  sin x
a  a 
2  3 
3  sin  x
a  a 

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Since the particle in a box is a quantum mechanical problem we

need to evaluate the most probable location of the particle in a box
and its energies at different permitted state.

Wave functions and Probabilities

Let us consider the three lowest energy solutions:
Case (1): n=1
This is the ground state and the particle is normally found in this
state. For n=1, the Eigen function is
2  
1  sin  x
a a
In the above equation  =0 for both x=0 & x=a. But 1 has a
maximum value for x=a/2.
2   a 2 2
1  sin   and  12 
a a2 a a

Ψ1

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

A plot of 1
2
the probability density versus ‘x’ is as shown. From
the figure, it indicates the probability of finding the particle at
different locations inside the box.
 1 =0
2
at x = 0 and x = a, also 1
2
is maximum at x = (a/2).
This means that in the ground state the particle cannot be
found at the walls of the box and the probability of finding the

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particle is maximum at the central region. The Energy in the ground

h2
state is given by E1  .
8ma 2

Case (2): n=2

This is the first excited state. The Eigen function for this state is
2  2 
given by 2  sin x
a  a 
Now, 2 =0 for the values x  0, a 2 , a and 2 reaches maximum

for the values x  a 4 , 3a 4 These facts are seen in the following

.
plot.

2

From the figure it can be seen that

2
2  0 at x = 0, a 2 , a and  2  2 / a at x  a 4 , 3a 4
2

This means that in the first excited state the particle cannot be
observed either at the walls or at the center. The energy is E2  4E1 .
Thus the energy in the first excited state is 4 times the zero point
energy.

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Case 3: n =3.
This is the second excited state and the Eigen function for this state
is given by
2  3 
3 
sin  x
a  a 
Now, 3 =0 for the values x  0, a 3 , 2a 3 , a

2
and 3 reaches maximum at x  a 6 , a 2 , 5a 6
a

3
2
3
a
2
xa x0 xa
x0 a a 2 a 5a a a a 2a 5a
6 3 3 6 6 3 2 3 6

3 =0 for the values x  0, a 3 , 2a 3 , a and 3 reaches maximum

2 2

2/a at x  a 6 , a 2 , 5a 6 at which the particle is most likely to be

found. The energy corresponds to second excited state is given by
E3  9E1 .

2. Free Particle:
Free particle means, it is not under the influence of any kind of
field or force. Thus, it has zero potential, i.e., V=0 over the entire
space. Hence Schrodinger’s equation becomes,

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2 8 2 m
 E  0
x 2 h2
h   2 
    E
8 2 m  x 2 
The above equation holds good for a particle for which the
potential V=0 over the entire space (no boundaries at all).

Since, for a free particle, V=0 holds good everywhere, we can

extend the case of particle in an infinite potential well to the free
particle case, by treating the width of the well to be infinity, i.e., by
allowing a =  .
We have the equation for energy Eigen values for a particle in an
n2h2
infinite potential well as, E  . Where n=1, 2, 3…
8ma 2
2a
Rearranging, we have, n 2 Em
h
Here, we see that, for a particle with constant energy E but
confined in the well ’n’ depends solely on ‘a’. In the limiting case
when a =  , it also follows that n =  , which essentially means
that free particle can have any energy Eigen values or possible
values of energy are infinite in number. Hence as, a   , n   .
Keeping in mind the energy level representation, we say that the
permitted energy values are continuous not discrete.

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Q.No Sample Questions CO

1. State De Broglie hypothesis. 1
2. What is wave function? Give its physical significance 1
and properties.
3. State Heisenberg’s uncertainty principle. By applying 1&2
Heisenberg’s uncertainty principle, illustrate the
broadening of spectral lines.
4. What are Eigen functions and Eigen values? 1
5. Setup time independent one-dimensional Schrodinger’s 1
wave equation for a matter wave.
6. Apply the time independent Schrodinger’s wave 1&2
equation to find the solutions for a particle in an
infinite potential well of width ‘a’. Hence obtain
normalized wave function.
7 Solve the Schrodinger’s wave equation for a free 1&2
particle.
8 Set up the differential equation for a particle in a 1D 2
well of finite depth and arrive at an Eigen Value
expression.

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PNo. Problems CO
1. Calculate the de Broglie wavelength associated 3
with a proton moving with a velocity equal to
(1/20)th of the velocity of light.
To be found: de Broglie wavelength, λ
Solution:
h 6.625 1034
   2.64 1014 m
mv 1.67 10  (1/ 20)  310
27 8

2. An electron and a proton are accelerated through 3

the same potential difference. Find the ratio of
their de Broglie wavelengths.
To be found: Ratio of de Broglie wavelength, λ
Solution:
De Broglie Wavelength, λ
h 1
 ,  
2mE m
1
For electron, e  For proton,
me
1
p 
mp

e mp
Ratio of De Broglie Wavelengths,  
p me

3. Compare the energy of a photon with that of a 3

neutron when both are associated with
wavelength of 1Ao. Given that the mass of
neutron is 1.67  10-27kg.

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To be found: Comparison of energy of photon

with that of neutron
Solution:
Energy of neutron,
P2 h2 (6.625 1034 )2
En   2   13.11021 J
2m 2 m 2  (11010 ) 2 1.67 1027
=0.082eV
Energy of photon,
hc 6.625 1034  3 108
Ep    19.89 1016 J
 110 10

=12421.9eV
E
Ratio of energies, p 1.5148 105
En
4. An electron has a speed of 4.8 x 105 m/s accurate 3
to 0.012 %. With what accuracy with which its
position can be located.
To be found: Uncertainty in position, Δx
Solution:
h
Uncertainty principle is given by, xp 
4

Uncertainty in speed,
0.012
Δv = 4.8 x 105 x = 57.6m/s
100
Uncertainty in position,
h 6.625 1034
x   1106 m
4 mv 4  3.14  9.11031  57.6

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5. The inherent uncertainty in the measurement of 3

time spent by Iridium-191 nuclei in the excited
state is found to be 1.4x10-10 s. Estimate the
uncertainty that results in its energy in the excited
state.
To be found: Uncertainty in energy, ΔE
Solution:Uncertainty principle is given by,
h
E t 
4
h 6.625 1034
E    3.77 1025 J
4t 4  3.14 1.4 10 10

6. The position and momentum of 1 keV electron 3

are simultaneously determined and if its position
is located within 1Å. What is the percentage of
uncertainty in its momentum?
To be found: Percentage of uncertainty in
momentum of electron, Δp
Solution:
h
Uncertainty principle is given by, xp 
4
Uncertainty in momentum,
h 6.6251034
p    0.53 1024 kg.m / s
4x 4  3.14 110 10

Momentum,
p  2mE  2  9.11031 11016 1.707 1023 kgm / s
Percentage of uncertainty in momentum of
p
electron, 100  3.1
p

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7. Show that the energy Eigen value of a particle in 3

second excited state is equal to 9 times the zero
point energy.
To be found: Energy Eigen value for second
excited state is equal to 9 times the zero point
energy.
Solution: Energy Eigen value equation is given
n2 h2
by, E 
8ma 2
h2
n=1, zero-point energy state, E1 
8ma 2
9h 2
n=3, second excited state, E3   9 E1
8ma 2
8. An electron is bound in a one-dimensional
potential well of width 1Å, but of infinite height.
Find the energy value for the electron in the
ground state.
To be found: Energy Eigen value
Solution:
Energy Eigen value equation is given by,
n2 h2
E
8ma 2
For n=1, ground state energy,
 6.625 10  34 2

E1   37.65eV
8  9.110  10 
31 10 2

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9. An electron is bound in one dimensional potential

well of infinite potential of width 0.12 nm. Find
the energy values in the ground state and also the
first two exited state.
To be found: Energy Eigen value
Solution:
Energy Eigen value equation is given by,
n2 h2
E
8ma 2
For n=1, ground state energy,
 6.625 10  34 2

E1   26.16eV
8  9.110   0.12 10 
31 9 2

For n=2 and 3,first and second excited state,

E2  4 E1 104.61eV E3  9 E1  235.44eV
10. An electron is trapped in a potential well of a
width 0.5nm. If a transition takes place from the
first excited state to the ground state find the
wavelength of the photon emitted.
To be found:
Wavelength of the photon emitted, λ
Solution:
For n=1, ground state energy,

E 
 6.625 10  34 2

 2.411019 J  1.507eV
8  9.110   0.5 10 
1 31 9 2

For n=2,first excited state,

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E2  4 E1  9.64 1019 J  6.025eV

Energy difference,
E  E2 – E1  7.23 1019 J  4.518eV

Wavelength of the photon emitted ,

hc 6.625 1034  3 108
   274.8nm
E 7.23 1019 J

Things to think about! (CO3)

1. Taking Planck’s law as the starting point derive Rayleigh –
Jeans law in the limit of high λ.
2. How can we naturally reconcile the dual Wave and Particle
nature of matter?
3. Is there any connection between the position – momentum and
energy-time uncertainty relationship? Discuss.
4. Is the derivation for particle in a box done above valid for
highly energetic relativistic particles? Discuss.
5. With respect to the particle in a box problem, find out what is
tunneling. What is its utility in different engineering domains?

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