Chapter 1

WAVE-PARTICLE DUALITY AND WAVE MECHANICS

1.1 Wave-Particle Duality of Radiation and Matter
The phenomena of interference and diffraction arise due to the
superposition of light waves and are produced by the interaction of light with
light. These phenomena provide conclusive evidence that light is a transverse
wave. However, several important phenomena such as black-body radiation,
photoelectric effect and the Compton effect result from the interaction of light
with matter and cannot be explained by the classical wave theory or the
electromagnetic theory of light.
To account for these observations, Max Planck in 1900 proposed a
bold hypothesis that radiant energy is emitted and absorbed in discrete
packets called quanta or photons, marking the beginning of the quantum
theory of radiation. Consequently, light or any electromagnetic radiation is
now understood to possess a dual nature: it exhibits wave character when
interacting with waves, as in interference and diffraction, and particle
character when interacting with matter, as in the photoelectric and Compton
effects. However, light never exhibits both characters simultaneously in a
single experiment.
By analogy with radiation, it was suggested that matter should also
possess a dual nature. This idea was first proposed in 1924 by the French
physicist Louis de Broglie, who extended the wave-particle concept to all
material particles in motion and postulated that every moving particle is
associated with wave properties. This hypothesis led to the development of
wave mechanics. The wave nature of matter can be reconciled with its particle
nature through the concept of a wave packet, formed by the superposition of
waves of different wavelengths, which represents a particle localized in a
small region of space.

1
2 Quantum Mechanics

The ideas of Planck and de Broglie were further developed between

1925 and 1930 by scientists such as Werner Heisenberg, Erwin Schrodinger,
Paul Dirac and others, leading to the formulation of quantum mechanics, the
fundamental theory governing physical phenomena at atomic and subatomic
scales.

1.2 Einstein’s Photoelectric Effect

The photoelectric effect is a phenomenon that fundamentally changed
the classical concept of light. The emission of electrons from a metal surface
under the action of light was first observed experimentally by Heinrich Hertz
in 1887 and later studied in detail by Philipp Lenard in 1900. The
experimental results could not be explained by classical wave theory and were
successfully interpreted by Albert Einstein in 1905 using Max Planck’s
quantum hypothesis.
Experimental Arrangement:

The experimental arrangement consists of an evacuated glass tube

containing two electrodes connected to an external circuit, as shown
schematically in figure. The anode is a metal plate whose surface is irradiated
by monochromatic light of known frequency. When light falls on the metal
surface, photoelectrons are emitted.
A variable potential difference is applied between the electrodes such
that the cathode is kept at a negative potential with respect to the anode. Some
of the emitted photoelectrons possess sufficient kinetic energy to overcome
the retarding potential and reach the cathode, thereby constituting a
measurable current in the external circuit. As the retarding potential is
increased, fewer electrons reach the cathode and the photocurrent gradually
Wave-Particle Duality and Wave Mechanics 3

decreases, finally becoming zero at a particular value of the stopping

potential.
Experimental Observations:
The following observations are made from the experiment:
1. Photoelectric emission occurs only when the frequency of the incident
light is greater than a certain minimum value, called the threshold
frequency  0 .
2. No photoemission occurs for frequencies below  0 , irrespective of
the intensity of light or duration of illumination.
3. Photoelectric emission is instantaneous when light of frequency
greater than the threshold frequency falls on the metal surface.
4. For incident light of frequency greater than  0 , the photocurrent
increases with increase in intensity of light.
5. The stopping potential, and hence the maximum kinetic energy of the
emitted photoelectrons, increases with increase in the frequency of the
incident light.

1.2.1 Einstein’s Explanation of the Photoelectric Effect

Einstein explained the photoelectric effect by proposing the particle
nature of light. According to Planck, light consists of discrete packets of
energy called photons, each having energy,
E  h
where h is Planck’s constant and  is the frequency of the incident radiation.
A photon transfers its entire energy to a single electron in the metal.
A part of this energy is used to overcome the binding energy of the electron
in the metal, known as the work function W and the remaining energy appears
as the kinetic energy of the emitted electron. Thus, the maximum kinetic
energy of the photoelectrons is given by
Emax  h  W  h(  0 )
where W  h 0 .

1.2.2 Implications of Einstein’s Photoelectric Equation

1. Since the kinetic energy of photoelectrons must be positive, no
emission occurs for    0 .
2. The maximum kinetic energy of photoelectrons is directly
proportional to   0 .
3. An increase in light intensity at a fixed frequency increases the
number of incident photons and hence the number of emitted
4 Quantum Mechanics

electrons, resulting in an increased photocurrent. However, the kinetic

energy of the photoelectrons remains unchanged.
4. As energy transfer takes place through direct interaction between
photons and electrons, the emission of photoelectrons is
instantaneous.
The photoelectric effect can be satisfactorily explained only by
considering the particle nature of light. This experiment provides strong
evidence for the wave-particle duality of light, demonstrating that light,
though commonly described as a wave, also exhibits particle-like behaviour
under suitable conditions.

1.3 De Broglie Hypothesis

In 1924, Louis de Broglie proposed a revolutionary hypothesis that,
since nature exhibits symmetry and simplicity in physical phenomena, all
material particles should possess both wave and particle characteristics, just
as radiation does.
For a photon, the energy E and momentum p are related by,
E  pc
According to quantum theory, the energy of a photon is also given by,
E  h  
From wave theory, the angular frequency  is related to the wave
number k by,
  ck
where c is the speed of the wave. Combining these relations,
pc    ck
 p  k
Since the wave number k  2 /  , the wavelength associated with a
particle of momentum p is
h

p
This wavelength is known as the de Broglie wavelength. In terms of
energy, the de Broglie wavelength of a particle of rest mass m0 and kinetic
energy E is,
h

2m0 E
Wave-Particle Duality and Wave Mechanics 5

1.3.1 Davisson-Germer Experiment (Experimental Verification of

Matter Waves)
The first direct experimental evidence for matter waves was provided
by the Davisson-Germer experiment, conducted by Clinton Davisson and
Lester Germer in 1927.

In this experiment, electrons emitted from an electron gun were

accelerated through a potential difference of V and directed onto a large single
crystal of nickel. The intensity of the scattered electrons was measured at
different angles using a movable detector. It was observed that the intensity
of scattered electrons showed sharp maxima and minima at certain angles.
These angular positions were found to depend on the energy of the electrons
and hence on the accelerating voltage. The pattern closely resembled a
diffraction pattern, similar to that produced by waves.

Davisson and Germer interpreted the regular arrangement of atoms in

the nickel crystal as a diffraction grating for electron waves, leading to
constructive and destructive interference.
6 Quantum Mechanics

(1) Explanation Using Matter Waves:

In a particular experiment, electrons were accelerated through a

potential difference of 54 V and a strong intensity maximum was observed at
a scattering angle of 65°. The interplanar spacing of the nickel crystal,
determined using X-ray diffraction, was found to be
d  0.91 Å

(2) Wave Treatment:

Since diffraction is a wave phenomenon, electrons are treated as
waves. For constructive interference between waves reflected from adjacent
crystal planes, Bragg’s condition is satisfied:
2d sin   n
For first-order diffraction ( n  1 ),
  2d sin 
Putting the experimental values, we have
  2  0.91 sin 65o  1.65 Å

(3) Comparison with de Broglie Wavelength:

The de Broglie wavelength of an electron accelerated through a
potential V is given by,
h 12.264
  Å
2m0eV V
For V  54 Volts,
12.264
  1.67 Å
54
Thus, the wavelength calculated from diffraction pattern matches with
de Broglie matter wave’s wavelength. This shows that the observed
diffraction pattern is due to the matter waves associated with scattered
electrons. The experiment, thus, confirms de Broglie hypothesis.
Wave-Particle Duality and Wave Mechanics 7

1.4 Classical Concepts of Particles and Waves

In classical physics, a particle is considered to be a localized object
having definite properties such as position, mass, velocity, momentum and
energy. Its motion is governed by Newton’s laws of motion, and at any given
instant it occupies a specific position in space.
A wave, on the other hand, is described by its periodic nature in space
and time. It is characterized by quantities such as wavelength, frequency,
amplitude and wave velocity. A wave can carry energy from one place to
another without any transport of matter. Unlike a particle, a wave is not
confined to a single point but is spread over a large region of space.
Thus, in the classical picture, particles and waves are treated as two
distinct and contrasting physical entities. A particle is localized and follows a
definite path, whereas a wave is extended and cannot be localized in space.
However, experiments in modern physics show that microscopic
entities such as electrons do not behave as purely particles or purely waves.
This raises an important question: if a particle exhibits wave properties, how
can a wave describe a particle that is localized in space? The answer to this
lies in understanding the difference between phase velocity and group
velocity, which together allow a wave description of a moving particle.

1.4.1 Propagation of Progressive Wave: Phase Velocity

The velocity with which the disturbance or planes of equal phase
travel through the medium is called phase velocity (or wave velocity).
A plane harmonic wave traveling along the positive x-direction is
given by,
2
y  a sin (ct  x )  a sin(t  kx)

where a is the amplitude,  ( 2 ) is the angular frequency and k ( 2 /  )
is the propagation constant (or wave number). The quantity (t  kx) is the
phase of the wave motion. A plane of constant phase (wavefront) is defined
by,
(t  kx)  constant
Differentiating this equation with respect to time, we have
dx
 k  0
dt
dx 
 
dt k
Thus, the phase velocity is given by,
8 Quantum Mechanics


vp   
k
Hence, phase velocity is the velocity with which planes of constant
phase advance through the medium.

1.4.2 Propagation of Matter Waves: Group Velocity

In practice, waves are not perfectly monochromatic. Instead, we
usually encounter wave packets, which are formed by the superposition of
several waves having slightly different frequencies and wavelengths. Such a
collection of waves is called a wave group.
When a wave group travels through a dispersive medium (a medium
in which wave velocity depends on frequency), different frequency
components travel with different phase velocities. As a result, the shape of
the wave group changes as it propagates.
The velocity with which the envelope of the wave group, or the point
of maximum amplitude, travels through the medium is called the group
velocity.

Formation of a Wave Group:

Consider two harmonic waves of equal amplitude but slightly
different angular frequencies 1 and 2 ; and the wave number k1 and k2 .
y1  a sin(1t  k1 x)
and, y2  a sin(2t  k2 x)
Their superposition gives
y  y1  y2
 a sin(1t  k1 x)  sin(2t  k2 x) 
 (  2 )t ( k1  k2 ) x   (  2 )t (k1  k 2 ) x 
 2a sin  1   cos  1  
 2 2   2 2
 (  2 )t ( k1  k2 ) x   (1  2 )t (k1  k 2 ) x 
 2a cos  1   sin   
 2 2 2 2
This represents a rapidly oscillating wave whose amplitude is
modulated by a slowly varying envelope. The envelope corresponds to the
wave group.
Wave-Particle Duality and Wave Mechanics 9

If a very large number of waves with wavelengths lying close to a

central wavelength 0 are superposed, the resulting disturbance forms a wave
packet, as shown in the figure. The wave packet consists of regularly spaced
maxima and minima, with the spacing equal to the central wavelength 0 .
Hence, the wavelength associated with the wave packet is 0 .
At the same time, the wave packet is
localized within a finite region of space at any
given instant. Therefore, such a wave combines
the characteristics of both a wave and a particle: it
exhibits wave-like periodicity through its
wavelength and particle-like localization through
its confined spatial extent.

Expression for Group Velocity:

The velocity with which the envelope (or wave packet) moves is given
by,
(  2 )
vg  1
(k1  k2 )
If the frequency components lie within a very small range, this
expression can be written in differential form as,
d
vg 
dk
This is the general expression for group velocity.

1.4.3 Relation between Group Velocity and Phase Velocity

Since   kv p where v p is the phase velocity, the group velocity
becomes,
d d (kv p ) dv
vg    vp  k p
dk dk dk
10 Quantum Mechanics

2
Now, since k  , we have

dk 2
 2
d 
 dv d  
 vg  v p  k  p 
 d  dk 
 2   dv p    
2
 vg  v p      
    d   2 
 dv 
 vg  v p    p 
 d 

1.5 Concept of Uncertainty Principle

The representation of a moving particle by a wave packet rather than
by a sharply localized point suggests that there is a fundamental limit to the
accuracy with which a particle’s position and momentum can be measured
simultaneously. If the wave packet is spread out, the wavelength associated
with it can be determined more accurately and hence the momentum is better
defined. However, in this case the particle’s position is uncertain, since it may
lie anywhere within the packet.
Thus, a decrease in the uncertainty x in position necessarily leads
to an increase in the uncertainty p in momentum, and vice versa. This
mutual limitation is not due to experimental imperfections but is inherent in
the nature of quantum systems.
Heisenberg formalized this idea by showing that the product of the
uncertainties in position and momentum of a quantum particle has a lower
bound. According to the Heisenberg uncertainty principle,
xp  
h
where   is the reduced Planck’s constant.
2

1.5.1 Uncertainty Principle and the Double-Slit Experiment

In the double-slit experiment, microscopic particles such as photons
or electrons are allowed to pass through two narrow slits and strike a
fluorescent screen. Although each particle arrives at the screen as a localized
point, the overall distribution of many such impacts forms an interference
pattern, which is a characteristic of wave behaviour. This shows that particles
are associated with matter waves.
Wave-Particle Duality and Wave Mechanics 11

Quantum mechanics predicts that interference occurs even when

particles pass through the apparatus one at a time. As expressed by Paul Dirac,
each particle interferes only with itself.
If an attempt is made to determine which slit the particle passes
through, the interference pattern disappears. This happens because observing
the particle at the slit disturbs its momentum, introducing uncertainty in it.
The resulting uncertainty in momentum leads to an uncertainty in the
particle’s position on the screen, comparable to the fringe spacing, thereby
washing out the interference pattern.
Thus, obtaining information about the particle’s path destroys the
interference pattern. This illustrates that precise knowledge of position and
momentum cannot be achieved simultaneously and provides a clear physical
demonstration of the uncertainty principle and wave-particle duality.

1.5.2 Complementarity Principle

According to the principle of complementarity, the wave and particle
aspects of light and matter are complementary in nature but cannot be
observed simultaneously. An experiment designed to show the wave
character, such as interference or diffraction, does not reveal the particle
character. On the other hand, experiments that demonstrate the particle
nature, such as those involving energy or momentum transfer, do not exhibit
wave behaviour.
Thus, the nature of the phenomenon observed depends on the
experimental arrangement. Both wave and particle descriptions are required
for a complete understanding of microscopic phenomena, although they are
mutually exclusive in any single experiment.

1.6 Physical and Probability Interpretation of the Wavefunction

In different types of classical waves, a definite physical quantity
varies periodically. For water waves, it is the height of the water surface; for
sound waves, it is the pressure and for light waves, the electric and magnetic
field components vary with space and time. This leads to an important
question: What is the quantity that varies in the case of matter waves?

1.6.1 Wavefunction
The quantity whose variation describes matter waves is called the
wavefunction, denoted by  . The wavefunction  ( x, y, z , t ) is associated
with a moving particle and depends on its position in space and the time of
observation. It provides information about the state of the particle.
However, the wavefunction  itself has no direct physical meaning.
This is because a physically observable quantity such as probability must
12 Quantum Mechanics

always lie between 0 and 1. The wavefunction, being a wave amplitude, can
take both positive and negative values, and even complex values, making it
unsuitable for direct physical interpretation.
This difficulty is resolved by considering the quantity |  |2 , the
square of the absolute value of the wavefunction. This quantity is always
positive and is known as the probability density.
According to the interpretation proposed by Max Born, the probability
of finding the particle at a point ( x, y, z ) at time t is proportional to the value
of | ( x, y, z, t ) |2 at that point and time. A larger value of | |2 indicates a
higher probability of finding the particle there, while a smaller value indicates
a lower probability.
As long as | |2 is not zero at a particular point, there exists a finite,
though possibly very small, chance of detecting the particle at that location.
Thus, while the wavefunction itself is not observable, its square determines
all measurable predictions regarding the position of a quantum particle.

1.7 Difference Between Classical (Newtonian) Mechanics and Quantum

Mechanics
In classical (Newtonian) mechanics, the future motion of a particle is
completely determined if its initial position and momentum are known, along
with the forces acting on it. In the macroscopic world, these quantities can be
measured with sufficient accuracy, and as a result, the predictions of
Newtonian mechanics agree very well with experimental observations. The
motion of a particle follows a definite trajectory, and physical quantities are
assumed to have precise values at all times.
Quantum mechanics, however, describes physical systems in a
fundamentally different way. Although it also establishes relationships
between observable quantities, the uncertainty principle places a fundamental
limit on the simultaneous determination of certain pairs of physical quantities,
such as position and momentum. As a result, the initial state of a particle
cannot be specified with complete accuracy. The more precisely the position
of a particle is known, the less precisely its momentum can be known and this
uncertainty affects the prediction of its future motion.
Therefore, quantum mechanics does not predict exact trajectories.
Instead, it deals with probabilities of finding a particle in a particular state or
at a particular position. The apparent certainty of classical mechanics is thus
an approximation that emerges in the macroscopic limit. For ordinary objects,
which consist of an enormous number of atoms, fluctuations from average
behaviour are negligibly small, making classical predictions appear exact. In
Wave-Particle Duality and Wave Mechanics 13

this sense, classical mechanics is an approximate limiting case of quantum

mechanics.

1.8 Background of Schrodinger Equation

The wave nature of matter is an inherent property of every particle.
One method of representing a particle in wave terms is through the
construction of a wave packet, which provides localization in space.
However, a wave packet spreads with time and therefore cannot permanently
represent a localized particle.
Quantum theory resolves this difficulty by introducing the concept
that every particle is described by a wavefunction, which depends on space
coordinates and time. The wavefunction contains all the information that can
be known about the physical state of the system.
In classical mechanics, the dynamical behaviour of a particle under
the action of forces is described by Newton’s second law, which is a
differential equation. Similarly, in classical electromagnetism, the behaviour
of electric and magnetic fields is governed by Maxwell’s equations, which
are also differential equations. Since particles exhibit both wave and particle
properties, it is natural to expect that the quantum mechanical wavefunction
should satisfy a suitable differential equation governing its evolution in space
and time.
This requirement led to the formulation of the fundamental equation
of quantum mechanics, known as the Schrodinger equation, which describes
the dynamical behaviour of quantum systems.

1.8.1 Time-Dependent Schrodinger Equation

The wave nature of matter suggests that the motion of a microscopic
particle cannot be described in terms of a definite trajectory, as in classical
mechanics, but must instead be represented by a wavefunction. The
fundamental equation governing the evolution of this wavefunction was
formulated by Erwin Schrodinger and occupies a central position in quantum
mechanics, playing a role analogous to Newton’s laws in classical physics.
Consider a particle of mass m, momentum p and energy E moving in
one dimension. The equation describing its motion must be consistent with
the de Broglie relation:
h h
  p
p 
According to Planck’s quantum hypothesis, the energy of the particle
is related to its frequency  by,
E  h
14 Quantum Mechanics

From classical mechanics, the total energy of the particle is the sum
of its kinetic and potential energies and is given by,
p2
E  V ( x, t ) … (1.1)
2m
where V ( x, t ) is the potential energy of the particle. Using   2 and
  2 / k , we have
h
E   
2
h
and, p k  k
2
Using these relations, eqn. (1.1) may be written as,
2 2
  k  V ( x, t ) … (1.2)
2m
In quantum mechanics, the state of the particle is described by a
wavefunction  ( x, t ). Unlike classical wave amplitudes, the wavefunction
need not be real and has no direct physical meaning. For a free particle
moving along the positive x-direction, a plane-wave solution may be assumed
in the form,
 ( x, t )  Aei ( kxt ) … (1.3)
Differentiating this wavefunction with respect to t, we have

 i Aei ( kx t )  i ( x, t )
t
i  ( x, t )
  … (1.4)
 t
Differentiating eqn. (1.3) with respect to x, we get
 ( x, t )
 ikAei ( kxt )  ik ( x, t )
x
  ( x, t )
2
 ( x, t )
and,  ik  ik  ik ( x, t )
x 2
x
 2 ( x, t )
  k 2 ( x, t )
x 2

1  2 ( x, t )
 k2   … (1.5)
 x 2
Putting eqns. (1.4) and (1.5) in eqn. (1.2), we get
 i  ( x, t )  2  1  2 ( x, t ) 
     V ( x, t )
 t  2m   x 2 
Wave-Particle Duality and Wave Mechanics 15

 ( x, t )  2   2 ( x, t ) 
 i     V ( x, t ) ( x, t )
t 2 m  x 2 
This equation is known as the time-dependent Schrodinger equation.
It governs the time evolution of the wavefunction and is the fundamental
dynamical equation of non-relativistic quantum mechanics. For motion in
three dimensions, the equation generalizes to,

 (r , t )   2 2   
i     V ( r , t )  ( r , t )
t  2m 
Introducing the Hamiltonian operator,
ˆ 2 2
H   V
2m
We have,

i  Hˆ
t
This equation governs the time evolution of the quantum state and is
the fundamental dynamical equation of non-relativistic quantum mechanics.

1.8.2 Probability Current Density and the Continuity Equation

According to the probability interpretation proposed by Max Born in
1926, the wavefunction  ( x, t ) does not represent a physical wave but instead
provides probabilistic information about the location of a particle. If, at a
given instant t, a measurement is made to locate the particle described by the
wavefunction  ( x, t ), then the probability P( x, t )dx of finding the particle
between the coordinates x and x  dx is given by,
P( x, t )dx   *( x, t ) ( x, t )dx |  ( x, t ) |2 dx
The quantity | ( x, t ) |2 is called the probability density. Since a
particle must be found somewhere in space, the total probability of finding it
over the entire space must be unity. In one dimension, this condition is
expressed as,


 |  ( x, t ) | dx  1
2


The time evolution of the wavefunction is governed by the time-
dependent Schrodinger equation,
   2  2 
i    V 
t  2m x 2

16 Quantum Mechanics

Taking the complex conjugate of this equation and assuming the

potential energy V to be real, we get
 *   2  2 
i     V  *
t  2m x
2

Multiplying the Schrodinger equation by  * and its complex
conjugate by  , and then subtracting the two resulting equations, we get
   *  2   2  2 * 
i  *    * 2   
 t t  2m  x x 2 
The LHS of this equation can be recognized as the time derivative of
the probability density |  |2 , while the RHS can be written as a spatial
derivative. Then,
      * 
( * )     *  
t 2mi x  x x 
P ( x, t )      * 
    *  
t 2mi x  x x 
Defining the probability current density S ( x, t ) as,
    * 
S ( x, t )   *  
2mi  x x 
The above equation may be written as,
P( x, t ) S ( x, t )
 0
t x
This equation is known as the continuity equation. It expresses the
conservation of probability in quantum mechanics and is directly analogous
to the continuity equation relating charge density and current density in
classical electrodynamics. In three dimensions, we can write

P(r , t )  
  . S (r , t )  0
t

1.8.3 Normalization of Wavefunction

According to the statistical interpretation of the wavefunction, the
quantity | |2 represents the probability density of finding the particle at
position x at time t. Since the particle must exist somewhere in space, the total
probability of finding it over the entire space must be unity. In one dimension,
this requirement is expressed by the condition:
Wave-Particle Duality and Wave Mechanics 17


 |  ( x, t ) | dx  1
2


The Schrodinger equation is linear in the wavefunction and its
derivatives. Consequently, if  ( x, t ) is a solution of the Schrodinger
equation, then A ( x, t ), where A is any constant, is also a solution. However,
not all such solutions correspond to physically acceptable states. The constant
A must be chosen so that the wavefunction satisfies the normalization
condition. The process of finding the appropriate value of the constant A such
that


 | A ( x, t ) | dx  1
2


is called normalization of the wavefunction. A normalized wavefunction
ensures that the total probability of finding the particle somewhere in space
is equal to unity and therefore represents a physically meaningful quantum
state.

1.8.4 Time-Independent Schrodinger Equation

In many physical situations, the potential energy V of a particle does
not depend explicitly on time. This is a good approximation for a large real
physical system, such as particles bound in atoms or confined in potential
wells.
When the potential V ( x, t )  V ( x), the time-dependent Schrodinger
equation allows solutions by separation of variables. The time-dependent
Schrodinger equation in one dimension is,
 ( x, t )  2   2  ( x, t ) 
i     V ( x) ( x, t ) … (1.6)
t 2m  x 2 
To solve this equation, we can use the method of separation of
variables. Then,
 ( x, t )   ( x) (t )
such that,
 d (t )
  ( x)
t dt
 d ( x)  2 d 2 ( x )
and,   (t )    (t )
x dx x 2 dx 2
Putting these values in eqn. (1.6), we get
d (t ) 2 d 2
i  ( x)    (t ) 2  V ( x) ( x) (t )
dt 2m dx
18 Quantum Mechanics

1 d (t )  2 1 d 2
 i   V ( x)
 (t ) dt 2m  dx 2
The LHS of this equation depends only on time, while the RHS
depends only on position. The equality can hold for all x and t only if both
sides are equal to the same constant. This constant is the total energy E of the
particle. Thus, we get two separate equations:
1 d (t )
i E … (1.7)
 (t ) dt
 2 1 d 2
and,   V ( x)  E … (1.8)
2m  dx 2
To solve eqn. (1.7), which is a first order differential equation in time,
we can write
1 iE
d   dt
 (t ) 
Integrating, we get
iE
log e    t

   e (iE /  )t
Again, multiplying eqn. (1.8) by  , we can write
 2 d 2 
 2
 V   E … (1.9)
 2m dx 
This equation is known as time-independent Schrodinger equation in
one dimension. It determines the allowed energy eigenvalues E and the
corresponding spatial wavefunctions  ( x) for a given potential.

Note:
For stationary states, the probability density is
P( x) |  ( x) |2
which is independent of time. The probability current density is,
    * 
S ( x, t )   *  
2mi  x x 
and, the wavefunction must satisfy the normalization condition:


 |  ( x) | dx  1
2


Wave-Particle Duality and Wave Mechanics 19

1.8.5 Conditions to be satisfied by a wavefunction

Due to the interpretations of | |2 as the probability density, the
solutions that can be allowed for  from the Schrodinger equation are
subjected to certain limitations. The most important limitations are
1.  must be finite for all values of x, y and z.
2.  must be single-valued i.e., for each set of (x, y, z),  must have
one value only.
3.  must be continuous for all regions except in those regions where
the potential energy V (x, y, z) is infinity.
  
4. The partial derivatives , and must be finite and
x y z
continuous everywhere.
A wavefunction which satisfies all the above-mentioned conditions is
called a well-behaved wavefunction.

NUMERICAL PROBLEMS

Problem 1: Find the energy of a photon having wavelength Å.

( h  6.62  10 34 Js ).
Solution: The de Broglie wavelength of photon is,
h

p
and, the momentum is,
h 6.62 1034 Js
p   6.62 1024 Jsm1
 1010 m
Hence, the energy of photon is given by,
E  pc  6.62 1024  3108  19.86 1032 J
 19.86  1032  6.24  1018 eV
 1.24 1024 eV

Problem 2: Electrons of 400 eV are diffracted through a crystal and a second

order maximum is observed where the angle between the diffracted beam and
incident beam is 30o. Calculate (a) the wavelength of the electron matter
wave, (b) the interplanar distance of those lattice planes which are responsible
for this maximum.
20 Quantum Mechanics

Solution: Given
Electron energy, E  400eV  400 1.602 1019 J  6.408 1017 J
Order of diffraction, n  2
Angle between incident and diffracted beam = 30o
(a) Electron wavelength,
h 6.626 1034
 
2mE 2(9.111031 )(6.408 1046 )
6.626 1034
  6.14 1011 m
1.08 1023
 0.614 Å
(b) In Bragg diffraction, the angle between incident and diffracted beams is
2θ.
2  30o
   15o
Using Bragg’s law,
n  2d sin 
 2(0.614)  2d sin15o
0.614
 d  2.37 Å
0.259

Problem 3: Calculate the de Broglie wavelength and the kinetic energy of

electrons which undergo first-order Bragg diffraction by a nickel crystal at an
angle of 30o. (Given: for Nickel, interplanar spacing is 2.15 Å)
Solution: Given
d  2.15 Å,   30o and n  2
Angle between incident and diffracted beam = 30o
(a) Using Bragg’s law,
n  2d sin 
   2(2.15)sin 30o
 l  2.15 Å

(b) We know that,

h

2mE
h2 6.626 1034
 E 
2m 2 2(9.111031 )(2.15 1010 )2
Wave-Particle Duality and Wave Mechanics 21

5.22 1018
 E  5.22 1018 J  eV
1.602 1019
 E  32.6 eV

Problem 4: For a wave travelling on the surface of water having phase

velocity proportional to the square root of its wavelength, show that the group
velocity is half of its phase velocity.
Solution: For a wave travelling on the surface of water, let the phase velocity
v p be proportional to the square root of the wavelength  . Thus,
vp  
 v p  C 1/2
where C is a constant. Differentiating with respect to  , we get
dv p C 1/2
 
d 2
The general relation between group velocity vg and phase velocity v p
in terms of wavelength is,
 dv 
vg  v p    p 
 d 
C
 vg  C 1/2     1/2
2
C
 vg  C  1/2   1/2
2
C
 vg   1/2
2
But since v p  C  1/2 , we get
1
vg  v p
2

Problem 5: Show that the phase velocity of a wave packet associated with a
particle moving with velocity v is greater than that of light.
Solution: For a wave with angular frequency  and wavelength  , we have
E  
h
and, p

Phase velocity,
22 Quantum Mechanics

 E
vp  
k p
If the particle described by de Broglie wave with wavelength  has
moving mass (relativistic mass) m when it travels with velocity v . According
to Einstein, E  mc 2 and p  mv .
mc 2 c 2
vp  
mv v
Here, the velocity of motion of the particle v  c , the above relation
shows that phase velocity is greater than speed of light. This, however, does
not contradict Einstein’s theory since no physical quantity like energy,
particle, signals, associated with the wave travels with the phase velocity.
These entities move with the group velocity.

Problem 6: Show that de Broglie wavelength for a material particle of rest

mass mo and charge q , accelerated from rest through a potential difference

of V volts relativistically is given by,

h

 qV 
2mo qV 1  2 
 2mo c 
Solution: The de Broglie wavelength of a particle is given by,
h
 … (1)
p
where p is the relativistic momentum of the particle.
A particle of rest mass m0 and charge q, accelerated from rest through
a potential difference V, acquires kinetic energy
K  qV
Hence, the total relativistic energy is,
E  m0 c 2  qV … (2)
According to the relativistic energy-momentum relation,
E 2  p 2 c 2  m02c 4
Putting eqn. (2) in this equation, we get
(m0c 2  qV ) 2  p 2 c 2  m02 c 4
 p 2c 2  (m0 c 2  qV ) 2  m02 c 4
 p 2c 2  q 2V 2  2m0 c 2 qV
Wave-Particle Duality and Wave Mechanics 23

q 2V 2
 p2   2m0 qV
c2
 qV 
 p 2  2m0 qV 1  2 
 2m0 c 
 qV 
 p  2m0 qV  1  2 
 2m0c 
Putting this value in eqn. (1), we get
h

 qV 
2mo qV 1  2 
 2mo c 
When qV  m0c 2 , the relativistic correction term becomes negligible
and the expression reduces to the non-relativistic de Broglie wavelength.

Problem 7: The wavefunction of a particle is given by   x   Ae  a x ,

2 2

  x   . Obtain the expression for normalization constant and the

probability of finding the particle in the region 0  x   .
Solution: The wavefunction of a particle is
  x   Ae  a x ,   x   .
2 2

(a) Normalization constant: The normalization condition is,



 |  ( x) | dx  1
2




 | Ae
 a 2 x2 2
 | dx  1



e
2 a 2 x 2
 A2 dx  1 … (1)

Using the standard Gaussian integral,


e
  x2
dx 


With   2a 2 ,


e
2 a 2 x 2
dx 

2a 2
24 Quantum Mechanics

Putting this value in eqn. (1), we get


A2  1
2a 2
2a 2
 A 
2


1/4
 2a 2 
 A 
  
(b) Probability of finding the particle in 0  x   :
The probability is given by,

P (0  x  )   | ( x) |2 dx
0

P  A2  e 2 a x dx
2 2

0
2 2
Since the function e2a x is even,
 
1 1 
0 
2 a 2 x 2 2 a 2 x 2
e dx  e dx 
2  2 2a 2
Thus,
1 
P  A2 
2 2a 2
1 2a 2 
 P 
2  2a 2
1
 P (0  x  ) 
2

eikr
Problem 8: Prove that for a wavefunction   , the probability current
r
v
density is J  , where v is the velocity of the particle.
r2
Solution: The probability current density is defined as,

J
2mi
*   * 
Since the wavefunction depends only on r, only the radial component
contributes. Then,
Wave-Particle Duality and Wave Mechanics 25


 
r
Thus,
  *   * 
J      … (1)
2mi  r r 
Given,
eikr eikr
 , * 
r r
 ike ikr
e ikr
and,   2
r r r
 *
ike ikr
eikr
and,   2
r r r
Putting these values in eqn. (1), we get
  eikr  ikeikr eikr  eikr  ikeikr eikr 
J   2     2 
2mi  r  r r  r  r r 
  ik 1 ik 1 
 J     2 
2mir  r r 2 r r
k
 J
mr 2
Using p  k  mv, we get
v
J
r2

Problem 9: Prove that for a wavefunction   Ae

i (xt )
, the probability
 2
current density is J  A where A is a constant.
m
Solution: The probability current density is defined as,

J
2mi
  *   * 
Since the wavefunction depends only on x, we have

 
x
Thus,
  *   * 
J    … (1)
2mi  x x 
26 Quantum Mechanics

Given,
  Aei (xt ) , *  Aei ( xt )

and,  i  Aei ( xt )  i
x
 *
and,  i  Aei ( xt )  i*
x
Putting these values in eqn. (1), we get
  *
J  (i )   (i * )
2mi 
 
 J 
 2i |  |2 
2mi

 J |  |2
m
Since |  |  A2 , we get
2

 2
J A
m

Problem 10: The wavefunction of a particle is given by ( x)  Ae

x
for
0  x   and  ( x)  0 elsewhere,  being real. Evaluate A in terms of
.
Solution: Given that,
Aex , 0  x 
(x)  
0, elsewhere
The normalization condition is,


 |  ( x) | dx  1
2


0 

 (0)dx   | Ae | dx  1
 x 2

 0


e
2 x
 A2 dx  1


 e  2 x 
 A  2
 1
 2  0
 1 
 A2  0   1
 2 
Wave-Particle Duality and Wave Mechanics 27

 A2  2
 A  2

MULTIPLE CHOICE QUESTIONS

1. The wave nature of electrons was experimentally verified by

(a) Compton scattering (b) Photoelectric effect
(c) Franck-Hertz experiment
(d) Davisson-Germer experiment
2. The group velocity of a matter wave packet corresponds to
(a) Phase velocity of the wave (b) Velocity of wave fronts
(c) Velocity of light (d) Velocity of the particle
3. The phase velocity of a matter wave associated with a free particle is
(a) Equal to group velocity (b) Less than particle velocity
(c) Greater than the speed of light
(d) Always equal to speed of light
4. A localized wave packet is produced by
(a) A single monochromatic wave (b) Standing waves only
(c) Reflection of waves
(d) Superposition of waves of different wavelengths
5. The time-independent Schrodinger equation is applicable to
(a) All non-conservative systems (b) Time-varying potentials
(c) Stationary states (d) Relativistic particles only
6. The equation of continuity in quantum mechanics represents conservation
of
(a) Mass (b) Energy
(c) Charge (d) Probability
7. For a free particle, the group velocity of the de Broglie wave is
(a) Twice the phase velocity (b) Equal to the particle velocity
(c) Greater than the speed of light (d) Zero
8. The time-dependent Schrodinger equation reduces to the time-
independent form when
(a) Energy is zero
(b) Potential is time-independent
(c) Particle is relativistic (d) Momentum is constant
9. Which of the following is NOT an acceptable wavefunction?
(a) Finite everywhere (b) Continuous
(c) Single-valued (d) Infinite at a point
28 Quantum Mechanics

10. The normalization condition of a wavefunction ensures that

(a) Total probability equals unity (b) Momentum is conserved
(c) Energy is quantized (d) Wavefunction is real
11. If the phase velocity of a matter wave is v p and group velocity is vg , then
for a non-relativistic particle
1
(a) v p  vg (b) v p  vg
2
(c) v p vg  c 2 (d) v p  c
12. A particle described by a sharply peaked wave packet has
(a) Large uncertainty in momentum
(b) Well-defined momentum and position
(c) Zero uncertainty in energy
(d) Infinite wavelength
13. If a wavefunction is real everywhere, the probability current density is
(a) Maximum (b) Finite and constant
(c) Zero (d) Imaginary
14. Which statement about phase velocity of matter waves is correct?
(a) It represents signal velocity (b) It violates causality
(c) It has no direct physical meaning (d) It equals particle velocity
15. If a wavefunction is multiplied by a real constant, the physical observables
(a) Always change (b) Change only for energy
(c) Change only for momentum
(d) Remain unchanged after normalization
16. The normalization of an eigenfunction of the Schrodinger equation
implies
(a) Energy quantization (b) Probability conservation
(c) Zero expectation value (d) Stationary state
17. The Schrodinger equation fails to describe particles accurately when
(a) Relativistic effects become significant
(b) Potential is time-independent
(c) Particle speed is much less than c
(d) Wavefunction is complex
18. A necessary condition for separation of variables in the Schrödinger
equation is
(a) Potential depends on momentum
(b) Potential is time-independent
(c) Energy is zero (d) Wavefunction is real
19. The Schrodinger equation describes deterministic evolution of
(a) Particle trajectory (b) Probability amplitude
(c) Probability density (d) Observable values
Wave-Particle Duality and Wave Mechanics 29

20. In quantum mechanics, time plays a different role from position because
(a) Time is quantized (b) Time is an operator
(c) Time is a parameter, not an operator
(d) Time is imaginary

ANSWER TO MCQ

1. (d) 2. (d) 3. (c) 4. (d) 5. (c) 6. (d) 7. (b) 8. (b) 9. (d) 10. (a)
11. (c) 12. (a) 13. (c) 14. (c) 15. (d) 16. (b) 17. (a) 18. (b) 19. (b) 20. (c)