WAVE MECHANICS

De Broglie hypothesis of matter waves

INTRODUCTION
Radiation is found to exhibit dual character. Some phenomena such as interference,
diffraction, polarization etc., are due to wave character of radiation. On the other hand,
phenomena such as photoelectric effect, Compton effect etc., could not be explained on the basis
of a wave theory. These latter phenomena exhibit the particle-like character of radiation. Thus
radiation exhibits a dual character, namely, a wave character and a particle – like character.
In Compton effect, monochromatic X-rays of wavelength  falling on a scatterer are
scattered into a different direction. At the same time, an electron ejected from the scattering
atom recoils in some other direction. It is found that the scattered X-ray has a wavelength ‟
which is longer than the incident wavelength . ‟ > .

Scattering atom
Scattered X-ray, ‟

P‟ = h /‟
Incident X-ray, 

P = h /
Recoiling electron,
P = P‟ + Pe pe

Compton assumed that X-ray photons have certain momentum and he treated the scattering of X-
rays as due to the inelastic collision between two particles – an X-ray photon and a scattering
atom.
The photon energy of a photon of frequency  is E = h ………….. (1)
According to Einstein‟s mass-energy relation, E = mc2 ………….(2)
where m is assumed to be the “rest mass” of the photon and c is the velocity of light.
From (1) and (2), we have, h = mc2 = mc.c ……… (3)
Treating mc as the “momentum” p of the photon, ie., mc = p, we have
h  p.c ……….. (4)
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c c h
Using   , in eqn. (4), we get h  p.c . Or p  …..(5). (on cancelling c )
  
Thus, a photon of wavelength  has an associated momentum p equal to h/ . When the
incident X-ray photon „collides‟ with an atom in the scattering target, it transfers some
momentum to an electron of the target atom. The electron recoils with momentum. pe. This
results in a decrease of momentum p of the X-ray photon on scattering. According to eqn.(5), 
is inversely proportional to p. So, there is an increase of the wavelength of scattered x-ray
photon.
De Broglie’s matter wave hypothesis
Considering the dual nature of radiation, de Broglie proposed that material particles may
also have a dual character similar to radiation. In other words, in addition to the discrete particle
behaviour, matter can have some wave-like character also. Such waves associated with moving
particles are called as “Matter Waves” or “de broglie waves”.
In support of his hypothesis, de broglie argued that
i) Nature loves symmetry.
ii) Matter and Radiation are the two great entities of the Universe. Radiation
possesses a dual character. Similarly the material particles may also have some wave
character in addition to their particle behaviour.
iii) By comparing the motion of a particle and the propagation of a wave, he stressed
that their behaviour is analogous to each other. De Broglie argued that Principle of least
action in mechanics and Fermat‟s principle of least transit time in optics are analogous to
each other.
Consider a particle moving from one point to another. According to Principle of least action, a
moving particle chooses a path in which the mechanical action is minimum‟
Consider a light ray moving from one point to another. According to principleof least transit
time, a light ray chooses a path for which the transit time is minimum‟

Thus, if radiation of wavelength  is assumed to have an associated momentum given by the

relation p = h / . , then the particle of mass m moving with a velocity v and momentum p
= mv has an associated matter waves of wavelength
 = h / p = h/mv. This wavelength of „matter waves‟ is also known as „de broglie
wavelength’.
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Wavelength of a free electron accelerated by an electrostatic field of potential V volts:

When a free electron of mass m is accelerated by an electric field of potential V volts, its
total energy which is purely kinetic is given by, ½ mv2 = eV ……(i)
Where e is the charge on the electron of mass m and v is its velocity.
Multiplying both sides of(i) by 2m, we get, m2v2 = p2 = 2meV (or) p = (2meV).
h h
Hence using de Broglie‟s eqn., we have,   ………. (ii).
p 2meV
For small accelerating potentials, v << c and hence mass of the electron will be equal to its rest
h h
mass, mo and hence , the de Broglie wavelength is    …….(iii).
p 2m0 eV
12.25
Substituting the values for h, mo ,and e, we have, AU ……… (iv)
V
For very large accelerating potentials (i.e., V is large), the velocity v of electron will be
m0
comparable to the velocity of light, c, and hence its relativistic mass m  is to be used in
v2
1 2
c
eqn.(i. The wavelength of electrons accelerated by a potential of about 100V is about
1.2 AU (using (iv)). This is comparable to X-ray wavelengths. Hence it was predicted that
similar to X-rays, electrons also would undergo diffraction by crystals since this wavelength is
comparable to the interatomic distances in crystals. Electron diffraction by crystals was first
observed by Davisson and Germer and later by GP Thomson. As diffraction experiments could
be explained only on the basis of a wave theory, this implied that the de Broglie‟s hypothesis on
dual nature of matter was verified experimentally.
deBroglie‟s dual nature of matter is not applicable to all material particles. It is relevant only to
microscopic paricles such as electrons, protons, atoms etc. It is irrelevant to macroscopic objects.
According to the principle of matter wave hypothesis, a free electron of mass 9.1x10-31Kg accelerated by
100Volts has a de broglie wavelength of about 1.2AU. Their wave nature could be experimentally verified
by electron diffraction by crystals. However, if we consider any moving macroscopic object (such as
cricket ball, bullet etc) its de broglie wavelength will be of the order of 10-30 AU or even lesser. This
wavelength is too small (0) to be experienced in any experiment. Hence the wave nature of matter is
irrelevant as far as macroscopic objects are concerned.
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HEISENBERG‟S UNCERTAINTY PRINCIPLE

Statement: The Total minimum uncertainty involved in the simultaneous measurement of a
pair of canonically conjugate variables cannot be less than ħ/2 (= h/4), where h is the
Planck”s constant.
Explanation: Consider a pair of canonically conjugate variables such as position x and x
component of momentum px . If x and px are the uncertainties in the individual measurements
of position x and momentum px , then the total uncertainty involved in their simultaneous
measurement is x . px .
Then according to Heisenberg‟s uncertainty principle, x . px  ħ/2 where ħ = h/2 .
Similarly Heisenberg‟s uncertainty principle relating y and py is y . py  h/4 and so on.
Heisenberg‟s uncertainty principle related to other similar pairs of variables are,
E . t  h/4.
where E is the uncertainty in the measurement of energy of an atom in an excited state and t
is the lifetime of the atom in that excited state. Similarly,
J .   h/4
where J is the total angular momentum of a particle and  is its angular position.
Proof for Heisenberg’s uncertainty Principle: 1. Gamma ray microscope expt.
Suppose it is desired to simultaneously determine both the position x and linear
momentum px of a free electron moving along x-direction. Let us imagine that a microscope with
a very high resolving power is used to accurately locate the position of the electron. The space
under the microscope objective is illuminated by appropriate

A B

+(h/)sin
-(h/)sin  

Electron x

O
h/
-rays

radiation photons. When the electron moves directly under the microscope, it will scatter some
of the photons. The scattered photons which enter into the microscope anywhere between OA
 5

and OB in the figure will form the image of the electron and thus the position of the electron is
found using the microscope. At the same instant the x-component of momentum of the electron
is measured using another device.
The microscope should have a very high resolving power so that the image of the „tiny‟
electron is formed in the microscope. The smallest separation d between two objects at which
their images are just resolved in the microscope is known as its „Limit of Resolution‟. Resolving
1
power (RP) of the microscope is the reciprocal of Limit of Resolution.  RP  . If  is the
d
semi-vertical angle subtended by the object at the objective of the microscope and  is the
wavelength of radiation used to illuminate the object, then

d = ……………(1).  Resolving power (RP) of the microscope is
2 sin 
1 2sin 
RP   ………… (2). This implies that, in order to have a very high
d 
Resolving power, one has to use radiation of very short wavelength (such as gamma-rays) for
illuminating the electron moving under the microscope.
The position of the electron can be determined with accuracy limited by the limit of
resolution of the microscope . i.e., Error (Uncertainty) in measuring the position can not be less
than the limit of resolution of the microscope.
 Minimum uncertainty (i.e., the smallest error) in finding the position of the electron is,

x  d  ……….(3)
2sin 
But the incident gamma-ray photon undergoes Compton scattering on „collision‟ with the
moving electron. This results in a momentum transfer between the electron and the colliding -
photon. Therefore, the electron suffers a change in its momentum, px. But the magnitude of the
change is not a constant and it depends on the direction in which the  –photon is scattered into
the microscope (between OA and OB).
The x-component of momentum of the electron will range from
 h   h 
 px  sin   to  px  sin   depending on the direction of gamma photon entering
     
into the microscope.
Uncertainty in the x component of momentum of the electron,
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 h   h  h
Δpx =   sin       sin    = 2 sin 

……….(4)
   
 The total uncertainty in measuring both position and momentum of an electron
simultaneously is, [using eqns. (3) & (4)],
x . px = (/2sin) . [ 2(h/)sin] = h
But h > h/4
x px > h/4.
This proves the Heisenberg‟s uncertainty principle

Proof for Heisenberg’s uncertainty Principle : 2. Electron Diffraction

Consider a stream of identical electrons of mass m flowing along x-direction with one
and the same velocity v. Then X-component of momentum of each electron is
px = mv. The Y-component of momentum, py, is zero. The de Broglie wavelength of the
electrons is =h/mv.

P = Px  Py  = p.sin
P = Px + Py

Y  Px  = p.cos

C1
A
O 
C Px = P ; Py= 0
px = p 
B
C2
 Py  = - p.sin
AB = b  Px  = p.cos

X
Suppose the electrons pass through a very narrow, vertical slit AB of width b. If the slit width b
is very small, the electrons suffer diffraction. The central, undiffracted maximum is observed at
C in the line of incidence. Let the first order minima due to the electron diffraction occur (at C1
and C2) on either side of the central maximum at an angle of diffraction  with the incident
direction. The condition for observing first order diffraction minimum at P1 is given by b sin =
.  b = /sin. The electrons entering anywhere within the width b of the slit causes the
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diffraction effect. Hence the uncertainty in the y-component of position of the electron is y =
b =/sin …… (1)
Before diffraction, the momentum of electron is px along x-direction and the y
Component of momentum py is zero. But after diffraction the electrons have Y-component of
momentum also as they form first order secondary minima at C1 and C2..
The y component of momentum of the Electron moving along C1 is psin and that
for the electron moving along OC2 is -psin. As an electron causing the diffraction pattern
may be diffracted in any direction between OC1 and OC2, the uncertainty
in the y component of momentum is
py = psin - ( -psin) =2psin = 2hsin/ ………………(2) [as p =h/]
The total uncertainty in position and momentum along y direction is
y.py = (/sin).(2hsin/) = 2h. As 2h > ħ , this implies that
y.py > ħ
-------------------------------------------------------------------------------------------------------
Significance of Heisenberg’s uncertainty principle: Heisenberg‟s uncertainty principle is a
consequence of dual nature of matter and vice versa.
Application of Heisenberg’s uncertainty principle
1. Applying the Heisenberg’s uncertainty principle, show that a free electron does not exists
inside an atomic nucleus
The radius of an atomic nucleus is of the order of 10 –14m. If a free electron were assumed
to be present inside the nucleus, it may be present any where within this linear dimension of the
atomic nucleus.
Uncertainty in the position of the electron in the nucleus, x = 10 –14m
According to the Uncertainty principle, x . p  ħ, where p is the uncertainty in
momentum. Assuming that the total uncertainty x . p  ħ,
Uncertainty in the momentum of the electron p = ħ / x = 1.05x10 –34 / 10 –14
i.e., p = 1.05x10 –20 Kg.m.s-1
Since this uncertainty in momentum is very large, the actual momentum of the electron, p,
cannot be less than p.  momentum of the electron , p  1.05x10 –20 Kg.m.s-1
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An electron moving with such a high momentum would have a very high velocity (i.e., relativistic
velocity) comparable to the velocity of light. C = 3x108 ms-1.
The energy of a relativistic electron is given by E =[ ( moC2 )2+ p2C2 ]
As ( moC2 )2 = (9.1x10-31)2x.(3x108)4 << p2C2 = (1.05x10 –20)2.(3x108)2, it is neglected.
E  pC = (1.05x10 –20) x.(3x108) / 1.6x10-19 = 1.97x107 eV  20 MeV
This is a very high energy since it is observed that  particles emitted during radioactive decay of
some nuclides have energies of the order of 4MeV only. This implies that electrons are not
present inside the nucleus.
[Note: The observed  decay in radioactive elements is actually due to the transformation of a
neutron into a proton plus an electron ( particle) plus a neutrino.
Therefore an electron is not present inside the nucleus in its own form but it is created at the
time of radioactive decay only]
------------------------------------------------------------
2. Determine the radius of Hydrogen atom in its ground state by applying Heisenberg’s
uncertainty principle.
Let r0 be the radius of hydrogen atom in its ground state and it is the minimum distance between
the electron and the hydrogen nucleus.
For any distance r from the nucleus, the uncertainty in the position of the electron in the
hydrogen atom is, x = r.
Applying Heisenberg‟s uncertainty principle, i.e., x.p  ħ, we have,
Uncertainty in momentum of the electron is p = ħ/x = ħ/r ….. (1)
As p is very large, the momentum p of the electron cannot be less than p and hence it can be
assumed that p  p = ħ/r ….. (2)
p2
the kinetic energy of the electron is given by T  where m is the mass of electron
2m
p2 ħ2
 using eqn. (2), we have, T   …………. (3)
2m 2mr 2
1 e2
The potential energy of the electron is V   . ……(4) [-e = charge on electron]
4 0 r

ħ2 1 e2
 Total energy of electron is E = T + V =  . …… (5)
2mr 2 4 0 r
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We know that E is minimum in the ground state where r = r0.

dE dE ħ2 1 e2
  0 at r = r0. As,  3  . , the above condition means that,
dr dr mr 4 0 r 2

ħ2 1 e2 ħ2 1 e2
  . 0   . . Rearranging we get,
mr03 4 0 r0 2 mr03 4 0 r0 2
ħ2 4 e0
r0   2 . Substituting the values of ħ,  0 , m and e, we get r0 = 0. 53 AU
m e

Substituting r = r0 = 0.53x10-10m and values of other constants in eqn. (5) we get

The total energy in ground state as E = -13.6eV. These values coincide remarkably with the
experimentally obtained values of ground state energy and radius of hydrogen atom
--------------------------------------------
Equation of motion for a wave : Classical Wave Equation
A general plane wave propagating along x-direction with velocity c may be represented by the
 2u 2  u
2
wave equation  c . 2 ……(1) , where u(x,t) = A exp[i(Kx-t)] is the instantaneous
t 2 x
amplitude of the wave at a point x in space, at an instant t. Here,  and  are the wavelength and
angular frequency of the wave respectively. K is the propagation vector or „wave vector‟ which
is directed along the direction of propagation. Its magnitude is K = 2/ . Angular frequency  is
related to frequency  by  =2.
The energy of the wave is proportional to A2 and .
SCHROEDINGER’S WAVE EQUATIONS IN ONE DIMENSION:
Equation of motion for Matter Waves
According to De Broglie‟s hypothesis, a moving particle of mass m and linear
momentum p has some kind of wave called ‘matter waves’ associated with it. The wavelength
of such matter waves (called „De Broglie wavelength‟) is given by the equation,
h
  ………..(2) .
p
Let (x,t) = A exp[i(Kx-t)] ……. (3) is the wave function representing the matter waves of a
particle of mass m moving in one dimension along x with linear momentum p = mv. In eqn
(3), K = 2/ ….. (a) and  = 2…… (b)
Consider ħK. Defining ħ = h/2 and using equation (a) first and then eqn.(2), we have,
 10

h 2 h
K .  p.
2  
p
Thus, linear momentum of the particle, p = ħK …… (4) (or) K ……….. (c)

The total energy of the particle is E = Kinetic energy + Potential energy = T+V
Also, the total energy E is related to a frequency , by E = h [Einstein‟s eqn]
h
Consider ħ . Substituting for ħ and , we have,   .2  h  E
2
E
Total energy of the particle, E = ħ  …..…. (5) (or)  ……..(d)

Substituting eqns.(c) and (d) in eqn (3), The wave function   (x,t) representing matter waves
i 
associated with a moving particle is    ( x, t )  A.exp   px  Et  
 
…………….. (6)
The total energy of the particle E is the sum of kinetic and potential energies. E = T + V.
The potential energy V may be (i) a function of both position x and time t. i.e, V  V (x,t)
or (ii) it may simply be a function of position only i.e, V  V (x).
In the first case, as V is a function of time, E also varies as a function of time. This is leads to a Time
Dependent Wave Equation.
In the second case, When V is independent of time, (i.e, V  V (x) only), the total energy E is also
independent of time. This leads to the Time Independent Wave Equation.
Time Dependent Wave Equation
Differentiating  in eqn (6) partially w.r.t. time t, we have,
  i  i
  A exp   px  Et    . .   E 
t   
 iE
i.e.,  . ……….. (7) { using eqn. (6)}
t

Multiplying both sides by ( i ħ ), we get i  E ……………… (8)
t
Eqn (8) is the Schroedinger’s Time dependent wave equation .

Schroedinger’s Time independent wave equation.

In the time independent wave equation, potential energy of the particle V is a function of
its position x in space only and also the total energy of the particle E is independent of time. So,
only the partial derivative of  with respect to space is considered.
Differentiating   (x,t) in eqn(6) partially w.r.t. x , we get
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  i  i ip i 
  A exp   px  Et    . . p  . A exp   px  Et  
x     
Differentiating this again partially w.r.t. x, we have,
 2 ip ip i   p2 i 
 . . A exp   px  Et   . A exp   px  Et 
x 2  
2
 
 2  p2
i.e.,  . ………………… (9) { using eqn. (6)}
x 2 2

 2
 2
 2 p2
Multiplying both sides of eqn. (9) by    , we have,  .  . …….. (10) But
 2m  2m x 2 2m
p2
the kinetic energy of the moving particle, T  . As E = T+V, T = (E –V).
2m
p2  2
  2
So, replacing in eqn. (9) by (E-V), we have   . 2   E  V  . . On
2m  2m  x
 2
  2
rearranging this, we get,    . 2  V  E ……………(11).
 2m  x
We know that when the potential energy V is V  V (x,t), the total energy E also varies as a
function of time. In this case eqn. (11) is Time Dependent Wave Equation. When it is only V  V (x),
then E is also independent of time. In this case eqn. (11) represents the Time Independent Wave
Equation.
First, considering V  V (x,t), and comparing eqn (11) with eqn.(8), we have,

 2
  2 
   . 2  V  E  i ………… (12)
 2 m  x t
Equation (12) is the general form of Schroedinger‟s time dependent wave equation.
When V is a function of only position independent of time i.e., V = V(x), the eqn. (11) becomes,
 2
 2
   . 2   x, t   V ( x).  x, t   E  x, t 
 2m  x
 2m 
Multiplying by   2  on both sides and rearranging
 
2 2m
  x, t   2  E  V ( x).  x, t   0 ………………….. (13)
x 2

Here, the total energy of the particle E is independent of time as V = V(x) only.
  (x,t) in eqn. (13) may be written as  (x,t) =  (x).f(t) …….(A)
where  (x) is a function of only x while f(t) is only a function of time t.
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2 2 2
Hence,   x, t     x  . f  t    f  t  .   x   …….(B)
x 2 x 2   x 2 
2 2m
Using eqns. (A) and (B) in (13), we get f (t ). 2   x   2  E  V ( x).  x  .f (t )  0 .
x
 2  x  2m
Canceling f(t) we get,  2  E  V ( x) .  x   0
x 2
Now, the entire equation involves only a single variable (namely, x), and hence partial
derivatives are irrelevant. Hence the above eqn. is written as
d 2 2m
 2  E  V   0  (14) with    ( x) and V  V ( x).
dx 2
This is the Schroedinger‟s time independent wave equation in one dimension.
========================================================
The Schroedinger’s time independent wave equation for a particle moving in three dimensions
is obtained by extending the one dimensional wave eqn to three dimensions. Here, we have to
consider the wave function  as   (r ) = (x.y,z) and the potential energy function as V 
V( r ) = V(x,y,z) where r  r(x,y,z). Further motion along one direction is not influenced by that
in other directions. Hence we have to consider partial derivatives once again. Thus
Schroedinger’s time independent wave equation in three dimensions is
 2 2 2 
 2  
 x y z 
2 2 
2m

 r  2  E  V r  . r
     0


i.e.,  2 r 
2m 
2   
E  V r  . r  0

 2 2 2 
where    2  2  2  is known as the Laplacian operator.
2

 x y z 
------------------------------------------------------------------------------------------------------------
How to use the Schroedinger‟s wave equations for physical problems?
 is the solution of the wave equation. Exactness of the solution depends on the correct
choice of the potential energy function V(x). In simple cases, it may simply be chosen from
similar physical problems already treated by classical mechanics.
For ex., in the case of one dimensional SHO, it is V = V(x) = ½ kx2.
In complicated problems, one has to choose them intuitively or by approximations or by a
combination of both. When the choice of V is proper, the solution  and the possible values of
energy E will be exact.
 13

-----------------------------------------------------------------------------------------------------------
Example for Time independent states of a system : Consider an electron moving in orbit in an
atom. As long as it moves in the same orbit it remains in the same state. This means that physical
variables such as total energy, angular momentum etc remain constant independent of time. Such
states are called stationary states. Stationary states are represented by different time independent
eigen functions and eigen values.
Example for Time Dependent states of a system: Consider a free electron moving in free space.
Its potential energy is zero. But, when it passes through regions of force fields (such as
electrostatic fields), it has a time dependent potential energy. The time dependence is due to the
variation of distance between the moving electron and source of the field. As V is time
dependent, the total energy E = T + V is also time dependent.
====================================================
Physical significance of the wave function and its interpretation:
 The wave function  is an abstract mathematical quantity. It is the solution of the
Schroedinger‟s wave equation. It gives a complete description of a moving particle.
 It represents the amplitude of the matter waves associated with a moving particle.
Physical meaning of Wavefunction, : It can be shown that speed vph (= /K) of matter
waves of a specific wave vector K (i.e., a monochromatic plane wave) is greater than the
velocity of light, c. This is physically unacceptable in any frame of reference. So, the wave
functions cannot be real and they could be complex or imaginary functions. Complex quantities
cannot be measured directly by any physical experiment. Therefore no real physical meaning is
attached to the wave function .
Physical interpretation (or)significance of wave function:
 No real physical meaning is attached to the wave function  as it may be complex.
However, the absolute square of the wave function is always real.
i.e, 2 = *. is real, where * is the complex conjugate of   (x)
 As 2 is real, Max Born interpreted it as the probability of locating the moving particle
at a given point in space. 2 is known as position probability density.
 In other words, if (x, t) is the wave function in one dimension, then, 2 represents
the probability of finding the particle per unit distance about the given point x.
 In three dimensions, 2 represents the probability of finding the particle per unit
volume around the given point x.
This interpretation is analogous to the intensity of a wave; If (x) is the instantaneous amplitude
of a wave at a point x, then the intensity „ I ‟ of the wave at x is I(x) = 2 = (x)*. (x) .
==========================================
 14

Normalisation of wave function

As the total probability is 1 (unity) always, the probability of locating a moving particle
(which is really existing and non-decaying with time) somewhere within the entire space is given
by,


 . .d  1 . Here  = (x,y,z) and d is the volume element = dx.dy.dz

*



This integral is called normalization integral. Wave functions of a moving particle which satisfy
this integral condition are said to be „normalized wave functions‟.

Conditions for a wavefunction to be a satisfactory solution of the Schroedinger’s wave eqn:

The probability interpretation of the wave function  imposes several conditions on the wave
function. They are
1) To be a satisfactory solution of the Schroedinger‟s wave equation, the wave function 
must be normalized. A normalized wavefunction satisfies the integral equation


 . .d  1 .
*



2) The wave function  must be single valued, finite and continuous in space.
3) It obeys all the standard boundary conditions.
4) Similarly, the first derivative of the wave function /x etc must also be single valued,
finite and continuous and obey the standard boundary conditions.
5) The wave function  representing a particle which is really existing cannot be zero
identically everywhere. [i.e., (x) cannot be zero at each and every point x in space.]
One dimensional space along x extends from - ∞ to +∞. For a truly existing particle (moving along
x), its wavefunction,(x) = 0 for each and every point x in space (between -∞ and +∞ ) is not
allowed; if allowed, it would make the probability density (x)2 = 0 everywhere. This refers to
the non-existence of the particle in space anywhere from - ∞ to +∞. So the wavefunction cannot be
zero everywhere in space. It has nonzero values at some points.
6) probability density (x)2 of locating the particle somewhere at x in space is nonzero.
Therefore is a convergent function in space. This means that (x)  0 as x  ∞. This condition is
imposed because a true moving particle occupies only definite positions in space. So  2 = 0 at x
= ∞, always.
EigenFunctions and EigenValues
The probability interpretation of the wave function  imposes several conditions on the
wave function. A wave function which obeys all these conditions represents one of the
characteristic states of the moving particle and it is known as an ‘eigen function’.
The physical variables such as energy E etc will also be characteristic of that state and
hence they are known as „eigenvalues’.
 15

The set of all eigenfunctions represents the different allowed states of the particle. The solutions
of Schroedinger‟s eqn., which are not eigen functions are physically unacceptable to represent the
particle and so they are discarded. Thus any physical system will have only a finite number of allowed
states.
-------------------------------------------------------------------------------------------------
APPLICATION TO SCHROEDINGER’s WAVE EQUATION
1. PARTICLE IN A ONE DIMENSIONAL POTENTIAL BOX
Consider a free particle of mass m moving in a region along the x-axis between x = 0
and x = L. The free particle has no potential energy in this region. V(x) = 0 between x=0 and x =
L. However, suppose there exist insurmountable potential barriers at x = 0 and x = L. So the
potential energy of the particle is infinite at these points., V(x) = ∞ at x=0 and x = L. The region
between x = 0 and x= L is termed as a „Potential box‟ with rigid walls at x=0 and x =L.
The finite energy of the particle will not be sufficient to surmount the infinite
Potentia barriers at the rigid walls. So whenever the moving particle reaches a wall, it is
reflected back and it starts moving in the opposite direction.
Hence the particle will bounce back and forth
Potential Energy,V
between the walls of the potential box and it
cannot be found outside the box. The general V = V =
Schroedinger‟s time independent wave equation
for a particle of mass m moving in one dimension
along x-axis is given by
d 2 ( x) 2m
 2  E  V  x    0 …….. (1)
dx 2
For the „particle in a box‟ problem, since
V(x) = ∞ at x=0 and x = L, the particle cannot be
found outside the box.
The wave function V=0

(x) = 0 at x  0 and x  L. …….(i) x=0 x =L

Further, the potential energy of the particle is zero within the box. Position, x

 V(x) = 0 for 0 < x <L…………………….(ii)

Using the conditions (i) and (ii), the appropriate Schroedinger‟s time independent wave equation
for the free particle moving inside the one dimensional potential box is given by
d 2 ( x) 2mE
 2   0 ............(2) for 0 < x < L [ using V = 0 for 0 < x < L ]
dx 2
 16

2mE
Let 2
= K 2 .............(3). Substituting this in eqn. (2), we have,

d 2
2
+ K 2 = 0 .................(4)
dx
To be a satisfactory solution of the wave equation, the wave function  obeys the following
conditions :  is single valued, finite, continuous and normalised. Also it must obey the
standard boundary onditions. The two boundary conditions for the particle in a box problem are ,
 ( x)  0 at x = 0 .................(5.a) and
 (x) = 0 at x = L ................. (5.b)
The general solution of the wave eqn. (4) is (x) = AsinKx + BcosKx ……….(6)
Here, A and B are unknown constants which can be determined by applying the boundary
conditions (5.a) and (5.b).
For applying the first boundary condition on (x), we replace x by 0 and write (x) = 0 in eqn
(6). Thus we have, (x) = 0 = Asin(0) + B. cos(0) = 0 + B.1  B = 0.
This implies that the second term (BcosKx) on the RHS of eqn.(6) is zero for all values of x
since the constant B =0.
The general solution in eqn. (6) is modified as
(x) = AsinKx …….…….(7) [using B = 0 in eqn. (6)]
The second boundary condition is (x) = 0 at x = L. Using this in the modified eqn. (7),
we get, AsinKL = 0 . This is true when KL = n
n
 K= ………………… (8) where n = 1, 2, 3, …. etc.
L
n = 0 is not allowed. The allowed solutions  of the wave equation are written as
 n 
 n  x   ASin  x ……… (9) with n = 1, 2, 3 …… etc.
 L 

n 2 2
.Squaring eqn. (8) we get, K 2 =
L2
2mE n 2 2 2 2
Substituting this in eqn. (3), 2
= K2 = (or) E= .n 2
L2 2mL 2

2 2
Rewriting this as En = 2
.n 2 ………… (10) with n = 1,2,3, ….
2mL
 17

2 2
h2
i.e., E1 = .1 2
 for n = 1  Ground state
2mL2 8mL2
2 2 2 h2
E2 = .2  .4 for n = 2  1st Excited state
2mL2 8mL2
2 2 2 h2
E3 = .3  .9 for n = 3  2nd Excitedstate etc.
2mL2 8mL2
These are the eigenvalues of energies of the free particle moving within a potential box. The
above eqns indicate that the energy eigenvalues are discreet.
------------------------------------------------------------------------------------------------------------
[Note: n = 0 is not allowed since this makes K = (n/L) = 0 and hence
(x) = AsinKx = 0 for all values of x (i.e., the wavefunction is zero identically everywhere). This would
mean that the particle is non- existent inside th epotential box.  n = 0 is not allowed]. This condition
also means that the ground state energy of the particle cannot be zero.
-----------------------------------------------------------------------------------------------------------
From eqn(9), the possible solutions to the wave equation are
 n 
 n  x   ASin  x where n = 1, 2, 3,….etc
 L 
To be satisfactory solutions of the wave eqn., the wave functions must be normalized. So,




n * n dx = 1.
L
As the particle exists only between x = 0 and L, we write this as  n * n dx = 1
0

*
 n   n 
L
 0  A sin L x    A sin
  L
x  dx = 1


 2n 
1-cos  .x 
 n 
L L
i.e., A2  sin 2  x dx = 1  A2   L  dx = 1
0  L  0
2

{ Sin2 = [(1 – cos2)/2] }

1 2n .x
L L
A2 L
i.e., A2    dx - A2  cos dx = 1  0 = 1
0  2  0
L 2

2 2
(or) A2   A
L L
 18

Using this in eqn. (9), we get the normalized eigen functions.

2 n x
n = .sin .............(10) with n =1, 2, 3,…etc. are the normalized eigenfunctions.
L L
2 x
i.e.,  1 ( x) = .sin for n =1,  Ground state
L L
2 2 x
 2 ( x) = .sin for n =2,  First excited state
L L
2 3 x
 3 ( x) = .sin for n =3,  Second excited state and so on.
L L
The energy levels, the shapes of eigen functions and corresponding probability densities are
shown in the figure for the first three states.

En n(x) n(x)2

3 32
E3= 9 (h2/8mL2)
n=3 n=3
n=3

22
2
E2=4 (h2/8mL2)
n=2
n=2 n=2

1
12
E1=1 (h2/8mL2)
n=1 n=1
n=1
0

x=0 x=L x=0 x=L

The probability of finding the particle within a small range x about the midpoint of a one
1 / 2  L  x 

   x .dx
2
dimensional potential box of width L is given by n
1 / 2 L  x
 19

2. QUANTUM MECHANICAL TUNNELING

Introduction: The phenomenon in which a free particle moving with energy E has a finite
probability (though very small) to pass through a potential barrier of energy U such that U > E
is termed as „Tunneling‟.
Tunneling is a quantum mechanical phenomenon. It has no classical analogue. This
becomes possible when (i) width of the potential barrier L is sufficiently small and (ii) E < U but
the difference between E and U is not large.

TUNNELING : CLASSICAL PICTURE

The total energy of a moving particle is E = T + V where T is the kinetic energy and V is the
potential energy. Consider a stream of identical particles each with energy E. Suppose they are
moving from the left (i.e, from region I) to the right. Let there be a potential barrier of height U

E < U
V=U

III
II
I

X=0 X=L
 20

between x = 0 and x = L (region II). According to classical mechanics, the particles can cross the
potential barrier only when E > U. But when E < U, they cannot enter the potential region
between 0 - L. This is because, when E < U, the kinetic energy of the particle T ( = E – U )
would be negative in that region which is physically unacceptable. So, all the particles with E <
U, when incident on the potential barrier at x = 0, would be reflected back into the region I. So,
the particles can never pass through the barrier (region II) and be found in the Region III.
However when this problem is treated wave mechanically it can be shown that a very
small fraction of the incident particles pass through it without any change in their total energy E.
and can be found in the Region III. This penetration of a potential barrier by a free particle
whose energy is less than the barrier height is termed as Tunneling.
Wave mechanical theory of Tunneling
Consider a a stream of identical free particles of mass m moving along x-direction from
left side to right side with a velocity v. Also, consider a potential barrier of width L extending
from x = 0 to x = L. The height of the potential barrier is V = U. Assume that the total energy of
the particle, E, is less than the potential barrier; E < U.
The Potential energy of the particle V(x) = 0 in both Regions I and III and V(x) = U in Region
II. i.e., V(x) = 0 for - ∞ < x < 0 (Region I) and for L < x < + ∞ (Region III)
V(x) = U for 0 < x < L (Region II)

V=U
I II III

I

III
II
V=0 V=0

x = - ∞ …… x=0 x=L ..… x = + ∞

 21

d 2 ( x) 2m
The general Schroedinger‟s wave equations is  2  E  V  x    0 ……(1)
dx 2
Let I, II and III be the wave functions in regions I, II and III respectively. The appropriate
Schroedinger‟s wave equations for the tunneling problem are obtained by substituting for  and
V in the three regions.
The wave moving from region I and incident (at x = 0) on the potential barrier is
oscillatory (drawn as thick lines in figure). A part of this wave is transmitted into barrier region
(Region, II). However it is not oscillatory, rather, it is a wave decaying exponentially. This is
because E < V in this region. If the width of the potential barrier is sufficiently small, it does not
decay to zero as it reaches the other end of the barrier at x = L. If so, then it enters Region III
with a non-zero amplitude and once again it becomes oscillatory. However, the amplitude of
oscillation is very small. A non zero wave amplitude in Region III is an indication that there is a
small probability for the particle to tunnel through the potential barrier even though E <V.
Solving the wave equations for the three regions, it can be shown that
16E  E  -2 L
Transmission coefficient or Tunneling probability, T   .1  .e …….. (2)
 U  U 
(or) T  e -2 L
 2m 
Where  is defined by  2   2  U  E  …………….. (3)
 
The probability for tunneling T would be large when both β and L have small values.
 2m 
As  2   2 U  E  ( eqn. 3), β will
  T
be small when (U-E) is very small. Thus
tunneling is appreciable when the width 1.0
of the potential barrier L is small and
the energy of the particle E is only
slightly less than the potential barrier U
so that E/U <1 but ( E-U) is very small. (E/U)
0.0
A plot of T vs. (E/U) is shown in figure.
0 1 2 3

(E < U) (E > U)
 22

TUNNEL DIODE
Tunneling is a quantum mechanical effect. Suppose a free microscopic particle of energy
E (such as electron, alpha particle etc) is incident on a potential barrier whose height U is such
that U > E. According to wave mechanics, the particle has a very small but finite probability to
pass through that barrier without any change in its energy. This phenomenon is known as
„Quantum mechanical Tunneling‟. According to classical mechanics this can never happen.
The wavefunction which is the solution of the Schroedinger‟s equation is an
exponential function of position inside the barrier (Region II ) and it decays fast. For very
narrow potential barriers, the wavefunction does not decay quite to zero before the other
end of the barrier is reached. The wavefunction stops decaying
at the boundary between region II and III
V =U>E
and it becomes oscillatory again in Region III.
As the wave function  is not zero in I
III
II
region III, 2> 0 and hence there is a finite
probability for the particle incident on one
side of the barrier to appear on the opposite side.
L

A tunnel diode is a pn junction in which

the impurity concentrations on both n and p
sides are very great (1020 cm-3). For such large impurity concentrations, the depletion
layer at the junction (Jn) is very narrow (10nm). These are called degenerate materials.
The Fermi level goes above the conduction band for n-type and below valence band for
p-type material(as shown in (A)).

P Jn N P Jn N P Jn N

C-Band Tunneling of
electrons
EF
EF
EF (holes) EF (holes) electrons electrons
EF (holes)
electrons EF C-Band C-Band
Electrons electrons
Electrons V-Band
V-Band
V-Band

(A) (B) (C)

Equilibrium (no bias ) + small forward bias - + large forward bias -

 23

At a small forward bias potential, EF shifts in opposite directions in P and N regions (See
(B)). So, electrons in the conduction band on n-side tunnel to the hole states of same
energy in the valence band on p-side. This produces a forward bias tunneling current (as
shown in (D)). With a larger bias voltage, the density of free electrons in the n-region
and the density of the empty states (holes) in the valence band of p-region also increase.
So, the tunneling current increases with increasing forward bias. It reaches a maximum
Im when the densities are maximum. As the forward bias continues to increase, the
number of electrons in the n side that are directly opposite to the empty states (holes) of
same energy in the valence band decrease (See (C)). Therefore decrease in the tunneling
current will start (See (D)) and it falls off to very low values for further increase in
forward bias. Unlike other diodes, a tunnel diode has a Negative Differential Resistance
(NDR) in this range. [ Resistance decreases with increasing bias voltage in the NDR Region]

Forward Bias current, I Tunnel diode

Im
N
D
Tunneling R
current
Ordinary pn junction diode

Forward Bias voltage, V

With further voltage increase, the tunnel diode I-V characteristic is similar to that of a
regular p-n diode
Under Reverse Bias
In this case the, electrons in the valence band of the p side tunnel directly towards the
empty states present in the conduction band of the n side creating large tunneling current
which increases with the application of reverse voltage. The TD reverse I-V is similar to
the Zener diode with nearly zero Break-down voltage.
Typical Tunnel Diode (TD) I-V characteristic
has two distinct features:
(1) it is STRONGLY non-linear Symbol of a
(compared to the resistor I-V).Current - Voltage tunnel diode
relationships for TDs cannot be described
using the Ohm‟s law
(2) it has a negative differential resistance (NDR) region.
 24

Applications of Tunnel Diodes

used as low-noise microwave amplifier, local oscillators for UHF television tuners,
trigger circuits in oscilloscopes high speed switches

Alpha Decay
The phenomenon of tunneling explains the alpha-particle decay of heavy, radioactive
nuclei.
Inside the nucleus, an alpha particle may be present as a nuclear particle. It feels the
strong, short-range attractive nuclear force as well as the repulsive Coulomb force.
The nuclear force dominates inside the nuclear radius (rN) where the potential is
approximately a square well. The Coulomb force dominates outside the nuclear
radius. The potential barrier at nuclear radius rN is about 25MeV. But the energy of
alpha-particle Ea is only between 4-9MeV. According to classical physics such a low
energy particle cannot cross the high energy potential barrier.

Energy

(Classically,
not allowed V
+ve to escape) E <V for r < r‟
E= V at r = r‟ Alpha Decay by Quantum Mechanical
Tunneling

E, Kinetic energy of alpha-particle

0
rN
r‟ = rN + L Radial distance, r

-ve

However, according to Gamow‟s Quantum mechanical theory of alpha decay,

1. an alpha particle may be present inside nucleus as a nuclear particle.
 25

2. It is in constant motion inside the nucleus. When it reaches the nuclear distance rN,
it is reflected back ibside by the potential barrier most of the times.
3. However, when treated quantum mechanically, the alpha-particle has some finite
probability to tunnel through the potential barrier, inspite of the greater height of the
potential barrier.
4. The tunneling probability is found to reduce with increasing height and width of
the potential barrier.

Applications of Quantum Tunneling

TUNNEL DIODE
A tunnel diode is a pn junction in which the impurity concentrations on both n and p sides are
very great (1020 cm-3). For such large impurity concentrations, the depletion layer at the junction
(Jn) is very narrow (10nm). At a small forward bias potential, electrons in the conduction band
on n-side tunnel to the hole states of same energy in the valence band on p-side. This produces
a forward bias tunneling current. Tunnel Diodes are used as low-noise microwave amplifier,
local oscillators for UHF television tuners, trigger circuits in oscilloscopes, high speed switches
etc.
Josephson Junctions
Josephson junctions consist of two superconductors separated by a very thin layer of non-
superconducting material. The superconducting current can tunnel across the barrier. The
electrical properties of this system are very precisely defined. Devices based on
Josephson junctions are used for high precision measurements.

Josephson junctions are common components in superconducting electronics, quantum

computers, and are also used extensively in superconducting quantum interference
devices (SQUIDs), which are capable of measuring extremely weak magnetic fields.

Scanning Tunneling Microscopes

A Scanning Tunneling Microscope (STM) allows for the imaging of the surfaces of
metals and semiconductors at the atomic level. It is developed by Gerd Binnig and
Heinrich Rohrer at the IBM Zurich Research Laboratory in 1982. The two shared half of
the 1986 Nobel Prize in physics for developing STM.
PRINCIPLE OF working of STM : Quantum mechanics allows a small particle, such as
an electron, to overcome a potential barrier larger than its kinetic energy. This is called
 26

tunneling. Tunneling is possible because of the wave-like properties of matter. Scanning

Tunneling Microscopes are based on the principles of tunneling.
A Scanning Tunneling Microscope (STM) works by scanning a very sharp
conducting probe across the surface of a material. An electrical current is passed down
the tip of the probe, and tunnels across the gap into the material. As the gap gets wider or
narrower, the tunneling current gets smaller or larger, respectively. Using this data, we
can build an incredibly detailed picture of the surface, even to the point of resolving
humps in the surface due to individual atoms. This technique has allowed leaps forward
in our understanding of the physics and chemistry of surfaces.
STM has fathered a host of new atomic probe techniques such as Atomic Force
Microscopy, Scanning Tunneling Spectroscopy, Magnetic Force Microscopy, Scanning
Acoustic Microscopy, etc.

Y
X

 The STM is an electron microscope that uses a single atom tip to attain atomic
resolution. An extremely fine conducting probe (with a sharp, single atom tip) is
mounted on a piezoelectric crystal tube. The tip is held above the sample at a
distance of an atomic diameter.
 Electrons tunnel between an atom on the sample surface and the tip, producing an
electrical signal. This the tunneling current is used as as a feedback signal,
 27

 While it slowly scans across the surface (along X-Y), the tip is raised and
lowered by Z-movement in order to keep the tunneling current signal constant and
maintain the distance between the tip-to- sample surface separation.
 The voltage that is necessary to keep the tip at a constant separation is used to
produce a computer image of the surface.
 This enables it to follow even the smallest details of the surface it is scanning.
 Tungsten is commonly used as probe material because you can use Electro-
chemical etching techniques to create very sharp tips like the one above.
 A STM does not measure nuclear position directly. Rather it measures the
electron
density clouds on the surface of the sample. In some cases, the electron clouds
represent
the atom locations pretty well, but not always.
USES
 Powerful imaging tool with unprecedented precision.
 Semiconductor surface structure, Nanotechnology, Superconductors, etc.
 In Nano Technology, STM tip is used as a tool for manipulating individual atoms
or molecules on substrate surface and directing them continuously to
predetermined positions
 Study of Spectroscopy of single atoms
 Limited biological applications: Atomic Force Microscopy
Advantages
No damage to the sample; Vertical resolution superior to SEM;
Spectroscopy of individual atoms can be studied

Xenon on
Nickel
Single atom lithography

Disadvantage of STM:
1. The STM can only scan conductive surfaces or thin nonconductive films and
small objects deposited on conductive substrates. It does not work with
nonconductive materials, such as glass, rock, etc.
 28

2. The spatial resolution of STM is fantastic, but the temporal resolution is typically
on the order of seconds, which prevents STM from imaging fast kinetics of
electrochemical process.
3. Making atomically sharp tips remains something of a dark art!
4. External and internal vibrations from fans, pumps, machinery, building
movements, etc. are big problems.
5. Ultra High Vacuum -
STM is not easy to built
and handle.

Iron on Copper

================ =================== ================

Physical constants
Planck‟s constant h = 6.626x10-34 J.s = 4.136x10-15 eV.s
h
ħ = = 1.055x10-34J.s
2
Mass of electron me = 9.11x10-31 kg
Mass of proton mp = 1836  me = 1.6726x10-27 kg
Mass of neutron mn = 1.675x10-27 kg
Electronic charge e = 1.602x10-19 C
Energy conversion: 1 eV = 1.602x10-19 J

Formulae:
* De broglie wavelength (or) Wavelength of matter waves of a moving particle of mass
h h
m with linear momentum p = mv is  = 
p mv
 29

For a particle moving with relativistic velocities (i.e., particle velocity v is comparable

 v2 
to the velocity of light), relativistic mass m  m0 1  2  should be used for
 c 
calculating 
h
* De broglie wavelength of a free particle of energy E is  
2mE
1 2 p2
(Note: Energy of a free particle E = mv   p  2mE )
2 2m

* De broglie wavelength of a free particle of mass M and charge q accelerated by an

h
electrostatic potential V is   ;
2MqV
h
* For a free electron of mass m and charge e accelerated by a potential V,  
2meV
h
* Heisenberg’s uncertainty principle for minimum uncertainty x.p 
2
Where Δx is uncertainty in position and Δp is uncertainty in momentum;
Δp = mΔv where Δv is the uncertainty in velocity
* Heisenberg’s uncertainty relation relating lifetime Δt of an excited state and the
h
uncertainty in the energy ΔE of the excited state is E  t 
2
 Eigenfunctions and Eigenvalues of energy of a free particle of mass m moving
within a one dimensional box of width L are:
2 n
Eigenfunction  n  .sin x
L L
n2 h2
Eigenvalues of energy En  where n = 1,2,3 …
8mL2
n = 1 for ground state, n = 2 for 1st excited state, n=3 for 2nd excited state and so on.

n x  2 n x
2

The Probability density,P =  = 2 



 
2 / L  Sin
L 
2
  Sin
L L
{ It is the probality per unit distance of finding the particle at a point x ( for one dimension);
It is the probality per unit volume of funding the paticle at a point, r ( for 3 dimension)}
 30

The probability of finding the particle in a stretch of dx is

n x  2 n x
2

P*dx =  * dx 2
=



 
2 / L  Sin
L 
2
  dx  Sin
L L
 dx

The probability of finding the particle over a range of x about the point x is

 x x / 2 
n x 
2

P= 

  
2 / L  Sin   dx
 x x / 2   L  x

x-x/2 x x+x/2

PROBLEMS:
1.Calculate the momentum of a photon of energy 1.77eV. [1eV=1.602x10-19J].
Solution:
Photon energy E = h = 1.77eV = 1.77x1.602x10-19J
Momentum of a photon, p, is given by
19
h h
E 1.77 1.602 10
p     9.56 1027 kgms 1
  c 2.998 108
(as h  E and  = c, the velocity of light in vacuum = 2.998x108 ms 1 )

 momemtum of photon of energy 1,77eV is p  9.46 1027 kgms1

2. Compare the energy of a photon with that of a neutron when both are associated
with wavelength of 1AU, given that the mass of neutron is 1.678x10-27kg (PEC, Dec
2015)

Wavelrngth ,  = 1 AU = 1x10-10m; mass of neutron = mn = 1.678x10-27kg

Energy of Photon of wavelength 1 AU is ,
8
hc 6.626 1034  3 10
E ph    1.99 1015 J
 110 10

Energy of neutron of wavelength 1 AU is,

   
2
h 34 2

  
p2 h 2 6.626 10
En    1.31 1020 J
2m 2  1.678  10  1 10  10 2
2 27
2m 2m
Eph / En = (1.99/1.31)x10+5 = 1.52 or Eph = 1.52 En

3. Calculate the de Broglie wavelength of an electron of energy 200 eV.

 31

Solution:
p2 h h
E (or) p  2mE  De Broglie waelength   
2m p 2mE
h = 6.626x10-34Js m = 9.1x10-31kg
E = 200 eV = E = 200 x1.602x10-19 = 3.204x10-17 J
h 6.626 1034
   
17
2mE
2  9.1x1031  3.204 10

4. Compute the debroglie wavelength of a 10keV proton. (mass of a proton is

1.675x10-27kg; Planck’s constant h is 6.62x10-34Js)
Solution:
Given: Mass of proton m = 1.675x10-27kg ; Energy of proton E = 10keV = 1x104 eV
(or) E = 1x104 x1.602x10-19 = 1.602x10-15 J h = 6.62x10-34Js
h 6.62 1034
 Debroglie wavelength of proton   
15
2mE
2 1.675 1027 1.602 10
=
5. Compute the de Broglie wavelength for a neutron moving with one tenth part of
velocity of light. (Mneutron = 1.674x10-27kg) (PEC, Dec.
2016)

6. Find the de Broglie wavelength of an electron which has been accelerated from rest
through a potential difference of 100V. (PEC, May 2017)

7. A bullet weighing 50 g is fired from a gun and it moves with a speed of 6.6 ms-1.
Calculate its de Broglie wavelength abd comment on it. Assume plancks constant h =
6.6x10-34J.s.
Solution:
Given :
Mass of bullet, m = 50g = 50x10-3kg = 0.05kg; speed of bullet = 6.6 ms-1

h = 6.6x10-34J.s. So, De Broglie wavelength  is

h h 6.6 1034
    2 1033 m  2 1023 AU
p mv 0.05  6.6

This wavelength is too small for any expt.

 32

8. An alpha particle is accelerated by an electric potential of 1000V. Assuming that

mass of a neutron equals the mass of a proton, compute the wavelength of matter
waves associated with the  particle using the data given below.
Mass of a proton is 1836 times that of an electron and mass of an electron is 9.1x10 -
31
kg; charge on a proton is 1.602x10-19C
Solution:
Given, mass of an electron me = 9.1x10-31kg and
Mass of a neutron mn = mass of a proton mp = 1836xme = 1836x9.1x10-31kg
As there are two protons and two neutrons in an  particle,
mass of alpha particle is m = 2(mn + mp) = 4mp =4x1836xme = 4x1836x9.1x10-31kg
Charge on an alpha particle is q = 2e = 2x1.602x10-19 C
Accelerating potential V = 1000 Volts
Energy of the  particle accelerated by a potential V is
E = qV = 2x1.602x10-19x1000 J =3.204x10-16 J
Planck‟s constant h = 6.626x10-34 J.s
h 6.626 1034
 Debroglie wavelength of the  paricle   
2m E  16

 
2  4 1836  9.11031   3.204 10 
 
=
9. An electron has a speed of 600 m/s with an accuracy of 0.005%.Calculate the
certainty with which its position can be located.
Solution:
Accuracy in measuring speed = 0.005%
Actual speed of electron V = 600m/s
0.005
 Error in measuring speed ΔV = 600   0.03 m/s
100
V  0.03m / s  Uncertaity in momentum p  m  V
Where, mass of an electron, m = 9.11x10-31Kg
According to Heisenberg‟s uncertainty principle,
h h
x.p  (or) x 
4 4  p
Where x is the uncertaity in position,
 33

6.626 1034
x   1.925 103 m
4  9.1110  0.03
31

10. The speed of an electron is measured to within an uncertainty of 2x104 m/s. What is
the minimum space required by the electron to be confined in an atom? (PEC, Dec.
2016)

11. The lifetime of an excited state of an atom is about 10-8 s. Calculate the minimum
uncertainty in the determination of the energy of the excited state of the atom.
Solution:
Heisenberg‟s uncertainty relation relating lifetime Δt of an excited state and the
uncertainty in the energy ΔE of the excited state is given by
h h
E  t  (or) E 
4 4  t
Given, Life time of the excited state Δt = 10-8 s.

Planck's constant h = 6.626  1034 J .s

h 6.626 1034
E    0.527  1027 J
4  t 4 10 8

12. A base ball of mass 200g is moving with a velocity of 3000cmper second. If its
position is located with an uncertainty of 1 micrometer, what will be the uncertainty in
its velocity. Comment on it.
base ball mass, m = 200g= 0.2kg; velocity, v = 3000cmper second = 30ms-1
x =1 micrometer = 1x10-6m
h h
x.p  or p  m  v  or
4 4  x
h 6.626 1034
Uncertainty in velocity, v   = 2.636x10-28ms-1
4  m  x 4  0.2 1106
This uncertainty in velocity is too small.
13. An electron is confined in a circular orbit of radius 0.5AU. Calculate the minimum
uncertainty in the momentum along any direction. ( mass of electron = 9.1x10031kg , h
= 6.626x10-34J.s ) (PEC, May 2015)

Assuming uncertainty in position x = radius of atom, x = 0.5AU = 0.5x10-10m ;

Using HUP,
 34

h h 6.626 1034
x.p  or p    1.055 1024 kg.m.s 1
4 4  x 12.566  0.5 10 10

14. Calculate the glancing angle at which electrons of energy 100 electron volts must
be incident on the lattice planes of a metal crystal in order to give a strong Bragg
reflection in the first order. Lattice spacing is given as 2.52AU.
Solution:
Energy of the electron, E = 100 eV = 100 x 1.602 x 10-19 J.
h 6.626 1034
 De Broglie wavelength,   
2mE 2  9.111031 1.602 1019
= 1.24 x 10-10 m.
The condition for Bragg reflection is 2dsinθ = nλ.
Lattice spacing, d = 2.52 x 10-10 m
n 11.24 1010
for n = 1, sin     0.246  θ =14.24 
2d 2  2.52 1010

15. Find the eigenvalues of energies and Eigenfunctions of an electron moving in a

one dimensional potential box of infinite height and 1 Å of width. Given that mass of
electron = 9.11 x 10-31 kg and h = 6.63 x 10-34 Js.
Solution:
2 n
Eigenfunction  n  .sin x
L L

n2 h2
Eigenvalues of energy En  where n = 1,2,3 …
8mL2
n = 1 for ground state, n = 2 for 1st excited state, n=3 for 2nd excited state and so on
Given that,
Width, L = 1Å = 1 x 10-10m ; m = 9.11 x 10-31 kg h = 6.63 x 10-34 Js
n2 (6.63 1034 )2
 En  31 10 2
  6.03 1019   n2 J ………. (1)
8  9.1110  (110 )
n = 1  corresponds to the state of least energy (ground state energy).
n = 2, 3,…..etc correspond to the first, second……. excited state.
 ground state energy, E1 = 6.03x10-19x12 = 6.03x10-19 J (Using n = 1 in eqn.(1))
Energy in the first excited state E2 = 6.03x10-19x22 = 6.03x10-19x4
 35

= 24.12x10-19J (Using n = 2 in eqn.(1))

Energy in the second excited state E3 =
6.03x10-19x32 = 6.03x10-19x9
=54.27x10-19J (Using n = 3 in eqn.(1))
and so on.

2 n
Eigenfunction  n  .sin x with n = 1,2,3, …….
L L
Assuming that x is in units of Å, substitute L = 1Å

2 1  x
Eigen function in the ground state (n=1) is 1  .sin  2 sin  x .
L L

Similarly, Eigen function in the First excited state (n=2) is  2  2.sin 2 x

Eigen function in the second excited state (n=3) is  3  2.sin 3 x

16. In the above problem, calculate the energy of excitation for transition from first
excited state to second excited state.
Solution:
h2
En   n2
8mL2
If En is the energy of state n and Em for the state m, then

h2
the excitation energy for transition from n  m is Em  En  (m2  n 2 )
8mL2
For 1st excited state, n=2 and for 2nd excited state n = 3
h2 h2
 E2   2 2
and E 3   32
8mL2 8mL2
 Energy of excitation for transition from I excited state to II excited state is
h2
 E3  E2     32  22 
8mL2
h2
 E3  E2    5  6.03 1019  5  3.015 1018 J
8mL2
17. A 5g marble is moving in one dimension within a box 50cm across. Find the
permitted energy at n=1 and n= 2. Comment on it. (Given that h = 6.63x10-34 J.s)
Solution:
Mass of marble m =5g = 5x10-3kg width of one dimensional box L = 50cm = 0.5m
 36

 6.63 1034 
2
h2 h2
Energy of particle En   n For n=1, E1 
2
 = 4.39x10-65J
8mL 2
8mL 8  5 10   0.5 
2 3 2

 6.63 1034 
2
h2
E2  n 
2
 4 17.56x10-65J
8  5 10   0.5 
3
2 2
8mL

These energies are very small. The difference between successive levels is also very
small (of the order of 10-65J) which can be approximated as zero. This means that though
the levels are discrete as their separation is small (nearly 0), the energy levels may be
approximated as continuous.
18. A particle is bound in a one dimensional potential well of width 1AUbut of infinite
wall height. Edstimate the probability of find over a stretch of 0.1AU each at distances
x = a/4, a/3 and a/2 and a from one end of the wall where a is the width of wall.
Consider the zero point energy state for the estimation. ( mass of electron =.11x10-31 kg
, h = 6.626x10-34 J.s) )
(PEC, Dec, 2015)
The probability of finding the particle in a stretch of dx is
n x  2 n x
2

P =  x dx
2 


=  2 / a  Sin  a 
2
  dx  Sin
a a
 dx

For n =1 (zero point energy state) , potential well of width a = 1AU and for a stretch of
dx = 0.1AU
2 n x 2 x
P = Sin2  dx  Sin 2  0.1 (or) P  0.2Sin2 x
a a 1 1
For x = a/ 4 = ¼ AU, P  0.2 Sin 2 1/ 4  0.1
For x = a/ 3 = 1/3 AU, P  0.2 Sin 2 1/ 3  0.15

For x = a/ 2 = 1/2 AU, P  0.2 Sin 2 1/ 2  0.2

For x = a = 1 AU, P  0.2Sin2 1  0

19. An electron is confined in a one-dimensional rigid box of length 1nm, is excited

from ground state to the 3rd quantum state, by an incident photon. Calvulate the
wavelength of the photon. ( mass of electron =9 .11x10-31 kg, h = 6.626x10-34 J.s )
(PEC, May 2015)
-31 -34
Given, mass of electron, m =9 .11x10 kg, h = 6.626x10 J.s
Length of potential box L = 1 nm= 1x10-9m
h2
Energy of particle of mass m , En   n2
8mL2
h2 h2
For n=1, E1   n 2
 1
8mL2 8mL2
 37

h2 h2
For n = 3, E3   n 2
 9
8mL2 8mL2
The energy of transition from n = 1 to n = 3 state is,
h2 h2 hc
E3  E1   (9  1)   8  h  (or)
8mL 2
8mL 2

hc hc mL2c [c = velocity of light]
  
E3  E1  h 2
 h
 2
8
 8mL 
mL2 c 9.1110  110   3 10
31 9 8 2

Wavelength,     4.124x10-7m
h  6.626  10 34

20. Calculate the first two energy levels of an electron cofined to a box 1AU wide.
(Given that h = 6.6253x10-34J.s and me = 9.1x10-31kg) (PEC, Dec 2015)

21. Explqain heisenberg uncertainty principle and find the minimum uncertainty of
position of an electron moving with a speed of 3x109m/s (PEC, May 2016)
h h
x.p  or p  m  v  or
4 4  x
Given speed of electron v = 3x109m/s . But this is greater than speed of light(3x108m/s )
and this is is physically not correct.. So uncertainty of speed of electron v can be assume
to be of the same order of v.
So assume v = 3x109m/s
h 6.626 1034
Uncertainty in position, x    m
4  m  v 4  9.11031  3 109

22. The width of an infinite potential well is 10AU. Calculate the first three energy
levels in terms of eVfor an electron. . (Given that h = 6.6253x10-34J.s and me = 9.1x10-
31
kg)
(PEC, May 2016)
2
h
Energy of particle of mass m in the state n is En  2
 n2 . n = 1,2,3 ……
8mL

23. An electron is bound in an one dimensional potential well of width 1AU, but of
infinite wall height. Find its energy values in the ground state and also in the first two
excited states. (PEC, Dec. 2016)
 38

24. Consider the following two free particles: i) An electron moving within a one
dimensional potential box of infinite height and width 10nm and ii) A marble of mass
10g rolling in a cylindrical tube of length 0.10m which is tightly closed at both the
ends. Treating them as quantum mechanical particles, calculate their energy and
velocity in their ground states. Compare the values and write your concluding
remarks. Given that Planck’s constant = 6.6x10-34j.S and mass of an electron = 9.1x10-
31
kg. (PEC, Dec. 2016)

25. An electron is confined to a one dimensional infinite potential well of width 0.2nm.
It is found that when the energy of the particle is 230eV, its eigen function has 5
antinodes. Find the mass of the particle. (PEC, May 2017)

The above figure is for n=3 state.

De Broglie waves form standing wave pattern between the rigid walls of the potential
box. n = 1,2,3, … etc states have 1, 2,3,…..etc no. of loops (or antinodes ) respectively.
no. of loops = no of antinodes ). Hence a state having 5 antinodes corresponds to n =5.

h2 h2
En   n 2
 m   n2
8mL2 8En L2
Given En =E5 = 230eV = 230x1.6x10-19 J with n= 5, L = 0.2nm = 2x10-10m
h = 6.626x10-34J.s Find m.

26. Consider a electron and a cricket ball Which of the two can undergo quantum
mechanical tunneling through a potential barrier. Why?
27. An electron is trapped in one-dimensional box of 0.1nm length. Calculate the
energy required to excite it from its ground state to the fifth excited state. (PEC, May
2018)
h2 h2
To find :( E6 – E1) E6  E1   (6  1 )  E6  E1 
2 2
 35
8mL2 8mL2

Additional Problems

1. A 1.00 g marble is constrained to roll inside a tube of length L = 1.00cm. The tube is
capped at both ends. Modelling this as a one-dimensional infinite potential box, determine
the value of the quantum number n if the marble is initially given an energy of 1.00 mJ.
Calculate the excitation energy required to promote the marble to the next available
energy state.
 39

28 -32
Ans : n = 4:27 x 10 , En+! – En = 4.69x10 J
This example illustrates the large quantum numbers and small energy differences associated with
the behavior of macroscopic objects.

2. Calculate the wavelength in nm of electrons which have been accelerated from rest
through a potential difference of 54V.

3. Show that the deBroglie wavelength for neutrons is given by λ = 0.286/ √V AU

where V is in electron-volts.

4. Applying the Heisenberg’s uncertainty principle, show that a free electron does not
exist inside an atomic nucleus

5. Determine the radius of Hydrogen atom in its ground state by applying

Heisenberg’s uncertainty principle.
( See Application of Heisenberg’s uncertainty principle, Pages 7-9)
6.. Write down the two Heisenberg uncertainty relations, one involving energy and one
involving momentum. Explain the meaning of each term. Estimate the kinetic energy
(in MeV) of a neutron confined to a nucleus of diameter 10 fm. [University of
London 2006]

7. A thermal neutron has a speed v at temperature T = 300K and kinetic energy 1/2mv2
= 3/2kT . Calculate its deBroglie wavelength. State whether a beam of these neutrons
could be diffracted by a crystal, and why?

8. Use Heisenberg’s Uncertainty principle to estimate the kinetic energy (in MeV) of a
nucleon bound within a nucleus of radius 10−15 m.

Short Answer questions

1. What are matter waves? (or) Write the DeBroglie hypothesis.

Electromagnetic radiation has a dual nature. In addition to the wave behavior, they show
discrete particle behavior also in experiments like Compton effect. de Broglie proposed
that material particles also can have a dual nature. According to de Broglie, moving
particles, in addition to the discrete particle behaviour, can have some wave-like
character also. Such waves associated with moving particles are called as “Matter
Waves” or “de broglie waves”.

2. Write the expression for de Broglie wavelength of a free electron accelerated by an

Electrostatic potential.
 40

de Broglie wavelength  of a free electron of mass m accelerated by an Electrostatic

h h
potential of V volts is given by    where h is the planck‟s constant
p 2meV
and e is the charge on the electron.

3. Matter wave hypothesis is not applicable for macroscopic objects. Why?

deBroglie‟s dual nature of matter is relevant only to microscopic paricles such as
electrons, protons, atoms etc. It is irrelevant to macroscopic objects. The de broglie
wavelength of free electrons is about a few AU. Their wave nature could be
experimentally verified by electron diffraction by crystals. However, if we consider any
moving macroscopic object (such as cricket ball, bullet etc) de broglie wavelength will
be of the order of 10-30 AU or even lesser. This wavelength is too small ( 0) to be
experienced in any experiment. Hence the wave nature of matter is irrelevant as far as
macroscopic objects are concerned.

4. State Heisenberg’s uncertainty principle

HEISENBERG‟S UNCERTAINTY PRINCIPLE: The Total minimum uncertainty involved
in the simultaneous measurement of a pair of canonically conjugate variables cannot be
less than ħ/2 (= h/4), where h is the Planck”s constant.

Is it possible to measure the energy and the momentum of a particle simultaneously with arbitrary
precision?

5. Explain Heisenberg’s uncertainty principle

If x and px are the uncertainties in the individual measurements of position x and
momentum px , then according to Heisenberg‟s uncertainty principle, the total uncertainty
involved in their simultaneous measurement is x.px and it is such that x . px  ħ/2
where ħ = h/2 .

6. What is the significance of Heisenberg’s uncertainty principle?

Heisenberg‟s uncertainty principle is a consequence of dual nature of matter and vice
versa. It facilitates the probability interpretation of the wave function.

7. What is a wavefunction?
The wave function  is an abstract mathematical quantity. It is the solution of the
Schroedinger‟s wave equation. It gives a complete description of a moving particle.
It represents the amplitude of the matter waves associated with a moving particle.
8. What is the physical meaning of the wavefunction 
It can be shown that speed v of matter waves of a specific wave vector K is greater than
the velocity of light, c. This is physically unacceptable in any frame of reference. So, the
 41

wave functions cannot be real and they could be complex or imaginary functions.
Complex quantities cannot be measured directly by any physical experiment. Therefore
no real physical meaning is attached to the wave function .
9. What is the physical significance(or physical interpretation) of the wavefunction?
No real physical meaning is attached to the wave function  as it may be complex.
However, the absolute square of the wave function is always real. i.e, 2 = *. is
real, where * is the complex conjugate of   (x)
As 2 is real, Max Born interpreted it as the probability of locating the moving particle
at a given point in space. 2 is known as position probability density. In other words,
if (x, t) is the wave function in one dimension, then, 2 represents the probability of
finding the particle per unit distance around the given point x.
In three dimensions, 2 represents the probability of finding the particle per unit volume
around the given point x.
This interpretation is analogous to the intensity of a wave; If (x) is the instantaneous amplitude of a wave
at a point x, then the intensity „ I ‟ of the wave at x is I(x) = 2 = (x)*. (x) .

10. What is meant by a ‘Normalised wave function’?

The total probability is 1 (unity) always. So the probability of locating a moving particle
(which is really existing and stable) somewhere within the entire space is given by,


 . .d  1 . Here  = (x,y,z) and d is the volume element = dx.dy.dz

*



This integral is called normalization integral. Wave functions of a moving particle which
satisfy this integral condition are said to be „normalized wave functions‟.

11. What are the conditions to be satisfied by the wavefunction ?

The probability interpretation of the wave function  imposes several conditions on the
wave function to be a satisfactory solution of the Schroedinger‟s wave equation. They are
1) The wave function  must be normalized. A normalized wavefunction satisfies the


 . .d  1 .
*
integral equation


2) It must be single valued, finite and continuous in space.

3) It obeys all the standard boundary conditions.
4) Similarly, the first derivative of the wave function /x etc must also be single
valued, finite and continuous and obey the standard boundary conditions.
5) The wave function  representing a particle which is really existing cannot be zero
identically everywhere. [i.e., (x) cannot be zero at each and every point x in
space.]
6)  is a convergent function in space. This means that (x)  0 as x  ∞.
 42

12. Write the Schroedinger’s time dependent and time indepencent wave equations.
The Schroedinger‟s time independent wave equation in one dimension is
d 2 2m
 2  E  V   0 with    ( x) and V  V ( x).
dx 2

The Schroedinger‟s Time dependent wave equation is i  E with    ( x, t ) .
t
13. What are eigenfunctions?
The probability interpretation of the wave function  imposes several conditions
on the wave function. A wave function which obeys all these conditions represents one
of the characteristic states of the moving particle and it is known as an ‘eigen function’.
14. What is meant by eigenvalues?
The set of all eigenfunctions represents the different allowed states of the particle. The
solutions of Schroedinger‟s eqn., which are not eigen functions are physically unacceptable to
represent the particle and so they are discarded. Thus any physical system will have only a finite
number of allowed states. The physical variables such as energy E etc of these allowed
states will also be characteristic of that state and hence they are known as „eigenvalues’.

15. For a particle moving within a one dimensional potential box, the quantum number
n=0 is not allowed. Why? (or)
Ground state energy of a free particle moving in a potential box is not zero. Why?
For particle in a box problem, n = 0 is not allowed since this makes K = (n /L) = 0.
Hence (x) = AsinKx = 0 for all values of x (i.e., the wavefunction is zero identically
everywhere). This would mean that the particle is not existing inside the potential box.  n = 0
is not allowed. This condition also means that the ground state energy of the particle cannot be
h2
zero since En  2
 n2 .
8mL
16. What is meant by tunneling?
Tunneling is a quantum mechanical effect. Suppose a free microscopic particle of energy
E (such as electron, alpha particle etc) is incident on a potential barrier whose height U is
such that U > E. According to wave mechanics, the particle has a very small but finite
probability to pass through that barrier without any change in its energy. This
phenomenon is known as „Quantum mechanical Tunneling‟. According to classical
mechanics this can never happen.
17. What are the conditions for a free particle to tunnel through a potential barrier?
The conditions for a free particle of energy E to tunnel through a potential barrier
of height U ( such that U > E) are
(i) width of the potential barrier L is sufficiently small and
(ii) U > E but the difference between E and U is not large.
18. What is a tunnel diode?
A tunnel diode is a pn junction in which the Symbol of a
tunnel diode
 43

impurity concentrations on both n and p sides are very

great (1020 cm-3). Very large impurity concentration
means that the depletion layer at the junction is very narrow
( about 10nm). For an electron from n-side to move into p-side in a p-n junction diode,
it should have sufficient extra energy to surmount the potential barrier. However, it is
found that the electrons tunnel through the barrier without any change of energy when a
very small forward bias is applied.
19. How is a tunnel diode different from an ordinary diode?
ordinaryJunction diode tunnel diode

Forward bias current is due to carrier For small bias voltages, the Forward bias
injection only current is due to tunneling
Differential resistance is +ve alwaya Differential resistance is –ve in tunneling
current region for currents > Im
Does not operate under reverse bias There is tunneling current in the reverse
bias also
20. What are the applications of a tunnel diode?
Tunnel Diodes are used as low-noise microwave amplifier, local oscillators for UHF television
tuners, trigger circuits in oscilloscopes, high speed switches etc.

Detailed Answer Questions

1.Discuss the de Broglie hypothesis of matter waves and derive an expression for the
wavelength of matter waves.
2. Derive an expression for the wavelength of matter waves of a free electron accelerated
by an electrostatic potential.
3. State, explain and prove Heisenberg‟s uncertainty principle.
Determine the radius of Hydrogen atom in its ground state by applying Heisenberg‟s uncertainty rinciple.
Applying the Heisenberg‟s uncertainty principle, show that a free electron does not exists inside an atomic
nucleus.
4. Derive Schroedinger‟s time dependent and time indepencent wave equations.
5. Write the physical meaning and interpretations of the wave function Explain the
conditions to be satisfied by the wavefunction to be a satisfactory solution of the
Schroedinger‟s wave equations.
 44

6. Discuss the problem of a free particle moving within a one dimensional potential box.
7. Write the appropriate Schroedinger‟s time indepencent wave equation for a free
particle of mass m moving in a one dimensional box between x = 0 and x= L. Solve it to
obtain the eigenfunctions and eigenvalues of energy.
8. Tunneling is a quantum mechanical problem. It has no classical analogue. Why?
Discuss the quantum mechanical tunneling..
9. Write a short note on working of a tunnel diode. What are its uses?
10. What is meant by tunneling? Explain its practical applications.
11. Discuss the principle construction and working of a STM.

2
k2  2 2 2
E=  .n
2m* 2mL2
2
kF 2
EF =
2m*
k
vF  F*
2m