Course: BPT-401 de Broglie Concept & X-ray Diffraction

de Broglie Concept of Matter Waves

In 1923, de Broglie proposed that wave-particle duality is not confined to light. Everything
made of some material exhibits wave-particle duality. Microscopic objects such as electrons,
atoms etc and the macroscopic objects like baseballs are the examples of such objects. The
behavior of relatively large objects, like baseballs, is dominated by their particle nature; to explain
the behavior of very small things like electrons, both the wave properties and particle properties
have to be considered. Electrons, for example, exhibit the same kind of interference pattern as light
does when they're incident on a double slit.

In this way, he suggested that the idea of dual nature (i.e., wave-particle duality) of light
should be extended to all microscopic particles. According to his hypothesis, a material particle
such as en electron, proton etc might have a dual nature just light does. He proposed that a moving
particle, whatever its nature, has wave properties associated with it. Thus, when a particle moves
in a medium, some waves of slightly different wavelengths are associated with it. A composition
of several waves of different wavelength can produce a wave packet. de Broglie also produced a
simple formula that the wavelength of a matter particle is related to the momentum of the particle.
So energy is also connected to the wave property of matter.
If a particle of mass ‘m’ has momentum ‘p’ and ‘’ the wavelength of the wave associated
with it then according to de Broglie’s hypothesis
h h
 
p mv
Where ‘v’ is the particle velocity
Derivation
According to Planck's hypothesis, the energy of a photon of frequency  is given by
E = h --- (1)
Where h is Planck's universal constant
But Einstein’s mass energy relation is
E = mc2 --- (2)
Where m is the mass of the photon.
Comparing (1) & (2), we have
h = mc2
hc
or  mc 2 {since c =  }

h
or  mc

h
or  --- (3)
mc
Since the nature of a moving particle is just like photon, hence for a particle moving with velocity
v, the above expression can be written as
h h
 
mv p
Where p = mv is the momentum of the particle.

Mentor: Dr. Neeraj Mehta

Course: BPT-401 de Broglie Concept & X-ray Diffraction

Matter waves or de Broglie waves

When a material particle moves in a medium a group of waves is associated with it due to
which it shows the wave-particle duality. These waves are known as Matter waves or de Broglie
waves.
According to de Broglie hypothesis, the wavelength of such a wave is given by
h h
  --- (1)
mo v p
Where
p = mv is the momentum of the particle
mo = mass of the particle
v = velocity of the particle
If E is the energy of the particle then we have
1 2 mo2 v 2 p2
E  mo v  
2 2mo 2mo
or p 2  2mo E
or p  2m o E --- (2)
From (1) & (2), we have
h

2mo E
If K be K.E. of the particle, then for its relativistic motion, we know that
E 2  p 2 c 2  mo2 c 4 --- (3)
& E  K  mo c 2 --- (4)
Eliminating ‘E’ from (3) & (4), we have
( K  mo c 2 ) 2  p 2 c 2  mo2 c 4
or ( K 2  2 Km o c 2  mo2 c 4 )  p 2 c 2  mo2 c 4
or ( K 2  2 Km o c 2 )  p 2 c 2
or K ( K  2mo c 2 )  p 2 c 2
or K ( K  2mo c 2 )  pc
K ( K  2m o c 2 )
or p --- (5)
c
Using (5) in (1), we get
hc

K ( K  2mo c 2 )
Explanation of Bohr’s quantization rule using de Broglie hypothesis
de Broglie adopted Bohr’s idea that electrons occupy essentially circular orbits, but he
assumed that the object occupying the circular orbit is a wave. The condition for these circular
systems is that when we go around the circle and follow the phase of the wave then we must arrive
back at the same phase as we started from, otherwise the wave would have a forbidden jump at
one point.

Mentor: Dr. Neeraj Mehta

Course: BPT-401 de Broglie Concept & X-ray Diffraction

This requirement (called boundary condition) implies that the length of the ring must be
exactly an integer multiple of a whole wavelength as shown in above figure . This is a so-called
periodic boundary condition. In other words the allowed wavelength are provided by the following
relation
n = 2πr
Proof:
According to Bohr’s theory the radius of the nth orbit is given by
 o n2h2
rn 
 me 4
Hence, the circumference of nth orbit is
2 o n 2 h 2
2 rn  --- (1)
me 4
The velocity of electron in nth orbit is given by
e2
vn 
2 o n h
The corresponding linear momentum of electron in n th orbit is given by
m e2
pn  m vn  --- (2)
2 o n h
The de Broglie wavelength associated with this electron is
h 2 o n h 2
n   --- (3)
pn m e2
Comparing Eq. (1) & (3), we have
2  rn
n 
n
or nn  2  rn --- (4)

This equation shows that the circumferences of orbits are integral multiple of the de Broglie
wavelength associated with the electron. Since, the electron does not radiate energy while moving
in the orbit, the de Broglie wavelength associated with it must be stationary wave in which no

Mentor: Dr. Neeraj Mehta

Course: BPT-401 de Broglie Concept & X-ray Diffraction

transfer of energy takes place.

The angular momentum of electron in its orbit is given by
m e2  on2h2
Ln  p n rn  .
2 o n h  me 4
nh
i.e., Ln  m vn rn  .
2
This is Bohr’s quantization rule.
Phase velocity and Group velocity
A group consists of a number of waves of slightly different frequencies superimposed upon
each other is called wave-packet. The velocity of each individual wave of a wave-packet is known
as phase velocity and it is denoted by vp. It is defined as

vp 
k
Where  is the angular speed and k the propagation constant of the wave.
The average velocity with which the wave-packet propagates in the medium is known as group
velocity, which is denoted by vg. Mathematically, it is defined as
d
vg 
dk
Relation between Phase velocity and Group velocity
By definition, phase velocity is expressed as

vp  or   kv p --- (1)
k
Then the group velocity is given by
d d dv p
vg   (kv p )  v p  k
dk dk dk
dv p d
i.e., v g  v p  k --- (2)
d dk
The propagation constant k in terms of wavelength can be expressed as
2
k --- (3)

Differentiating (3) w.r.t. , we have
dk d 2  2
 ( ) 2 --- (4)
d d  
Using ( 3) & (4) in Eq. (2), we get
2 dv p 2
vg  v p  ( )
 d  2
dv p
i.e., vg  v p  
d
This is the required relation between phase velocity and group velocity.
Dispersive and non-dispersive medium
A medium is said to be dispersive, if the phase velocity vp in this medium varies with
wavelength λ. Thus, in a dispersive medium, we have

Mentor: Dr. Neeraj Mehta

Course: BPT-401 de Broglie Concept & X-ray Diffraction

dv p
v p  f ( ) i.e., 0
d
A medium is said to be non-dispersive, if the phase velocity vp is independent of wavelength λ in
this medium. Thus, in a non-dispersive medium, we have
dv p
v p  f ( ) i.e., 0
d
In a non-dispersive medium, the phase velocity is equal to group velocity.
Phase velocity and Group velocity for a relativistic particle
Phase velocity vp and Group velocity vg in terms of energy ‘E’ and momentum ‘p’ can be expressed
as
  E
vp    --- (1)
k k p
d d ( ) dE
& vg    --- (2)
dk d (k ) dp
Where E   is the energy and p  k is the momentum of a particle moving with velocity v.
For relativistic motion of the particle, we have
E  mc 2 --- (3)
& p  mv --- (4)
Where m is the relativistic mass of the particle.
Using (3) & (4) in Eq. (1), we get
E mc 2
vp  
p mv
c2
or vp  --- (5)
v
Also, for a relativistic particle, the relation between relativistic energy and momentum is given by
E 2  p 2 c 2  mo2 c 4 --- (6)
Where mo is the rest mass of the relativistic particle.
Differentiating Eq. (6), we have
2 E dE  c 2 2 p dp
dE pc 2
or 
dp E
dE mvc 2
or  [using (3) & (4)]
dp mc 2
dE
or v --- (7)
dp
Using (7) in Eq. (2), we get
vg  v --- (8)
Equation (5) and (8) are the required expressions of the Phase velocity vp and Group velocity vg
for the relativistic motion of a particle.
Comparing (5) and (8), we get

Mentor: Dr. Neeraj Mehta

Course: BPT-401 de Broglie Concept & X-ray Diffraction

vg v p  c 2
Phase velocity and Group velocity for a non-relativistic particle
Phase velocity vp and Group velocity vg in terms of energy ‘E’ and momentum ‘p’ can be expressed
as
  E
vp    --- (1)
k k p
d d ( ) dE
& vg    --- (2)
dk d (k ) dp
Where E   is the energy and p  k is the momentum of a particle moving with velocity v.
For non-relativistic motion of the particle, we have
1
E  mo v 2 --- (3)
2
& p  mo v --- (4)
Where mo is the rest mass of the particle.
Using (3) & (4) in Eq. (1), we get
1
m v2
E 2 o
vp  
p mo v
v
or vp  --- (5)
2
Also, for a non-relativistic particle, the relation between energy and momentum is given by
p2
E --- (6)
2m o
Differentiating Eq. (6), we have
2 p dp
dE 
2mo
dE p
or 
dp mo
dE mo v
or  [using (3) & (4)]
dp mo
dE
or v --- (7)
dp
Using (7) in Eq. (2), we get
vg  v --- (8)
Equation (5) and (8) are the required expressions of the Phase velocity vp and Group velocity for
the non-relativistic motion of a particle.

Mentor: Dr. Neeraj Mehta

Course: BPT-401 de Broglie Concept & X-ray Diffraction

Failure of diffraction of X-rays from transparent gratings.

The phenomenon of diffraction of waves takes place only when the size of the object from
which diffraction takes place is of the order of wavelength of the waves.
The wavelength of visible light is of the order of 4000 Å to 8000 Å. To study the diffraction of
light we use transparent diffraction gratings having about 6000 lines per cm. Thus, a slit is formed
between two consecutive lines, giving rise to transparencies and opacities. The size of each
opacity or transparency is about 1.6 × 104 Å. This size is comparable to the wavelength of yellow
light which = 6000 Å = 0.6 × 104 Å.
In order to study the diffraction of X-rays it is necessary to have a grating, whose slit width
ranges from 0.1 Å to 100 Å. Such a fine grating is not available. On the other hand, it has been
observed that crystals have a regular arrangement of atoms in the crystal structure and the spacing
between adjacent lattice planes is comparable to wavelength of X-rays.
It is for this reason that crystals are used to study the diffraction of X-rays as transparent
gratings cannot be used for the purpose.

Diffraction of X-rays: Bragg's law

The wavelength of X-rays is very small; hence an ordinary diffraction grating cannot be
used to measure it. W.L. Bragg discovered that X-rays can be regularly diffracted by the parallel
atomic planes of the crystals when the rays are incident on their surface nearly at glancing angle.
Let us consider two atomic planes X1X2 and Y1Y2 of a crystal with inter-planar spacing ‘d’
as shown in Figure . Let S1A and S2B are the two parallel X-rays falling on atoms A and B of
atomic planes X1X2 and Y1Y2 respectively at angle of incidence ‘θ’. Let R1A and R1B are the
diffracted X-rays. Draw the perpendiculars AM and AN on S 2B and R2B. The intensity of the
diffracted X-rays R1A and R1B will be maximum, when the path-difference MBN between them
equal to an integral multiple of the wavelength λ of the X-rays.

R1
S1
R2
S2

θ A
X1 X2

d θ θ
M N
θ
Y1 Y2
B

Mentor: Dr. Neeraj Mehta

 Course: BPT-401 de Broglie Concept & X-ray Diffraction

Thus, the essential condition for constructive interference between the diffracted X-rays
R1A and R1B is
Path-difference MBN = n λ
i.e., (MB + BN) = n λ --- (1)
Where n = 1, 2, 3……………
In right angle ΔAMB and ΔANB, we have
sin θ = (MB / AB) = (NB / AB)
or MB = NB = AB sin θ
or MB = NB = d sin θ --- (2) [since AB = d]
Using (2) in (1), we get
(d sin θ + d sin θ) = n λ
i.e., 2 d sin θ = n λ
This condition is known as Bragg’s law. An X-ray of wavelength λ striking a crystal of inter-planar
spacing ‘d’ at an angle of incidence reflects only when the values of d, θ and λ satisfy the above
equation. Bragg’s law gives us the useful information about the structure of solids. Using this
equation, we can determine whether the given solid has amorphous structure or crystalline
structure.
Bragg’s Spectrometer
For the structural studies of
different crystals, W. H. Bragg and his son
W. L. Bragg designed an apparatus known S1 S2
as Bragg’s spectrometer. In this apparatus,
X-rays from an X-ray tube are allowed to D
pass through two slits S1 and S2 to obtain a
narrow beam, which is then allowed to fall
on a single crystal D mounted on a turn
table (see Figure ) The crystal is rotated C
to increase the glancing angle at which the
X-ray beam is incident at the crystal.
n=1
n=2
n=3
The position of table is noted on a circular vernier
n=4 scale. An ionization chamber C is used for
measuring the intensities of the diffracted X-rays
Ionization in terms of ionization current. The angle for
Current which diffraction intensities are maximum give
the value of ‘θ’ satisfying Bragg’s law
n λ = 2 d sin θ
n = 1 creates first order reflection, n = 2 creates
second order reflection and so on.
Glancing Angle Thus, we have
1 λ = 2 d sin θ1,
2 λ = 2 d sin θ2
and 3 λ = 2 d sin θ3
Where θ1, θ2 and θ3 are glancing angles for n = 1, 2, 3 etc respectively.
Hence sin θ1 : sin θ2 : sin θ3 = 1 : 2 : 3
Hence, by measuring glancing angles at which reflections occur, we can determine the inter-planar
spacing knowing the wavelength of the X-rays. For example, the structure of rocksolt (NaCl) was
studied by using Bragg’s spectrometer. If a graph is plotted between the ionization current and the

Mentor: Dr. Neeraj Mehta

Course: BPT-401 de Broglie Concept & X-ray Diffraction

glancing angle as shown in Figure , some peaks are obtained, which represents the values of
glancing angles satisfying Bragg’s law.

Davisson and Germer Experiment

In 1927, Davisson and Germer demonstrated the wave-nature of electrons by their
experiment. They set out to study the surface of metals, in particular, nickel. They intended to that
by scattering electrons of the surface of nickel and observing the scattered electrons. They used a
well collimated electron beam and observed electrons at well-defined angles. The apparatus used
by them is shown below in Figure.

Construction
A collimated beam of electrons is produced using an electron gun. This beam is incident
on a target of Nickel crystal. The electrons are scattered in all directions by the atoms of the target.
The intensity of the scattered electrons in a given direction is measured by allowing it to enter in
a collector, which can be moved along a circular scale.
Principle
If the material particles have a wave character, they are expected to show the interference
and diffraction phenomena. Davisson and Germer experimentally demonstrated the diffraction of
electron beam.

Heated Filament
Charged
plates Nickel crystal
Accelerated Electrons
φ

Circular
Detector scale

Working
Let an electron of mass m is accelerated by potential V then its kinetic energy is given by
1
K  mv 2  eV --- (1)
2
Where v is the velocity of the accelerated electron.
From Eq. (1), we have
2eV
v --- (2)
m
The wavelength of the de Broglie wave associated with this electron is expressed as
h
 --- (3)
mv

Mentor: Dr. Neeraj Mehta

Course: BPT-401 de Broglie Concept & X-ray Diffraction

Using Eq. (2) in (3), we have

h

2eV
m
m
h
i.e.,  --- (4)
2 e mV
Substituting m = 9.1 × 10-31 kg, e = 1.6 × 10-16 Coul & h = 6.62 × 10-34 J-sec in Eq. (4), we have
h 6.62  10 34 12.24
  or   Å
2 e mV 2  1.6  10 19  9.1  10 31  V V
Davisson and Germer calculated the de Broglie wavelength using two different approaches.
In the first approach, Davisson and Germer used de Broglie’s hypothesis. They plotted a
large number of polar graphs to show the variation in the intensity of electron beam with scattering
angle for different accelerating voltages. They found that a “bump” begins to appear in the curve
for V = 44 volts (See Figure ). With increasing potential, the bump moves upward and becomes
more prominent in curve for V = 54 volt at φ = 50o, thereby indicating the maximum scattering in
electron beam happens at φ = 50o for V = 54 volts.

Thus, for V = 54 volts, the de Broglie wavelength of the electrons is

Mentor: Dr. Neeraj Mehta

Course: BPT-401 de Broglie Concept & X-ray Diffraction

12.24 12.24
   1.66 Å --- (5)
V 54
In the second approach, Davisson and Germer calculated the de Broglie wavelength by treating
electron beam as a wave. They used Bragg’s equation n λ = 2 d sin θ.
For Nickel crystal, d = 0.91 Å. Also, θ = 65o.
Hence for first order (n = 1) reflection, we have
λ = 2 d sin θ = 2 × 0.91 × sin 65o = 1.65 Å --- (6)
The equations (5) and (6) show an excellent agreement between the two approaches. Thus,
Davisson-Germer experiment provides a direct verification of wave nature of electrons and hence
it also verifies de Broglie’s hypothesis.

Mentor: Dr. Neeraj Mehta