UNIT-1

ATOMIC AND MOLECULAR PHYSICS

SYLLABUS: Vector atom model and Stern-Gerlach experiment, Quantum numbers associated
with it, Angular momentum of the atom, Coupling schemes, Spectral terms and spectral
notations, Selection rules, Intensity rules, Fine structure of Sodium D-lines, Zeeman
effect,Experimental arrangement to study Zeeman effect;Raman effect, Characteristics of Raman
effect, Experimental arrangement to study Raman effect, Quantum theory of Raman
effect,Applications of Raman effect.

INTRODUCTION:
In nineteenth century, electron was first discovered by J.J. Thomson. It is negatively
charged particle. But the atom as a whole is electrically neutral. Hence it is clear that the atom
must contain +vely charged particle to balance the negative charge of the electron. This was
confirmed by the discovery of the proton. Thomson measured the ratio of e/m value. The charge
of electron was measured by Millikan oil drop experiment. The mass of the electron is found by
dividing charge e by the ratio e/m. Thomson showed that the mass of the electron is of the order
1/2000th of mass of hydrogen. But they do not know how the +ve and –ve charges are distributed
in an atom.
Scientists proposed several theories from time to time regarding the atomic structure. They are
(1) Thomson’s plum pudding model.
(2) Rutherford’s nuclear model.
(3) Bhor’s model.
(4) Sommerfield’s relativistic model
(5) Vector model and
(6) Wave mechanical model.
(1) THOMSON’S PLUM-PUDDING MODEL:
According to Thomson the +ve charge inside an atom is uniformly distributed through
out the entire atom. The negatively charged electrons were imagined to be embedded at different
places inside the continuous +ve charge as shown in the figure.

DRAW BACKS: According to Thomson, the emission of radiation occurs when the stable
distribution of electrons is disturbed and electrons start vibrating like oscillators. Hence emission
spectrum consists of a single line of 1400Ao.But we know that the atomic spectra of hydrogen
consists of several lines.
(2) RUTHERFORD’S NUCLEAR MODEL:
According to Rutherford’s model the atom consists of a
tiny massive, +vely charged nucleus surrounded at a relatively
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great distance by electrons as shown in the figure (from the experiment scattering of alpha
particles by thin metal foil).In this model the electrons can’t remain stationary because of the
electrostatic force of attraction by the positively charged nucleus. Hence the electrons were
revolving around the nucleus. The electrostatic force of attraction provides necessary centripetal
force for revolving of electrons. Hence there exist dynamically stable orbits.

DRAW BACKS: Here there is no restriction about the radius of the electron orbit. According to
classical electromagnetic theory any charged particle having accelerated motion must emit
energy radiation. Hence the electron should radiate energy continuously .so the electron looses
energy and spirals down and crashes in to the nucleus within 10-8 s .This gives continuous
spectrum but not line spectrum.
(3) BHOR’S THEORY:
Inorder to overcome the problem of instability of Rutherford’s planetary model of atom,
Bhor proposed that an electron revolving in an orbit such that its angular momentum is
quantalised will not radiate energy and the orbit will be stable. If the electron moves from one
orbit to another orbit then it emits or absorbs radiation.
DRAW BACKS OF BHOR’S THEORY:
(1) The theory could not explain the spectra of atoms more complex than hydrogen.
(2) The theory does not give any information regarding the distribution and arrangement of
electron in an atom.
(3) The theory does not explain the experimentally observed variations in intensity of the
spectral lines of an element.
(4) This theory can’t be used to calculate about transitions from one level to another.
(5) This theory can’t be used for the quantitative explanation of chemical bonding.
(6) The theory fails to give correct result when an electric or magnetic field is applied to the
atom.
(7) It failed to explain the fine structure of spectral lines.

According to Bhor’s theory of circular orbit, we get only a single line when electron
jumps from a higher orbit to a lower orbit but experimental results showed that the
H  , H  , H  lines of hydrogen atomic spectra are not single lines. For example H 
consists of five lines. This is called fine structure of spectral line.

(4) SOMMERFELD’S RELATIVISTIC MODEL:

In 1921 sommerfeld modified Bhor’s model by introducing the idea of “motion of
electron in an elliptical orbits and taking into consideration the variation of mass with velocity”.
ELLIPTICAL ORBIT:
According to sommerfeld, the electron
moving around the nucleus in an elliptical orbit
with the nucleus at one focus.In the elliptical
orbit the position of the electron at any time may
be fixed by two co-ordinates r and  where r is

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the radius vector and  is the angle between the radius vector and the major axis of the ellipse
which is called azimuthal angle. Consider an electron of mass m and linear tangential velocity v
revolving in the elliptical orbit. The tangential velocity of the electron can be resolved into two
components. One along the radius vector called radial velocity and the perpendicular to radius
vector called the transverse velocity. Corresponding to those velocities the electron has two
momenta called as radial momentum and the transverse momentum or azimuthal momentum.
Sommerfeld introduced the two quantum numbers nr and n called as radial quantum
numbers and azimuthal quantum numbers. Here nr + n = n , where n is called principal quantum
number.
Corresponding to n=1 there are two possibilities i.e., nr = 0, n = 1andnr = 1, n = 0 .when n = 0
the ellipse is converted into a straight line and the electron pass through the nucleus twice during
every period. This type of motion is not possible. Hence, the lowest possible value of n = 1 .
Therefore if n = 1 then n = 1 [s orbit]
If n = 2 then [p orbit]
n = 2 ( circularor bit )
n = 1 ( ellipse )

If n = 3 then [d orbit]
n = 3 ( circularor bit )
n = 2 ( ellipse )
n = 1 ( ellipse )
These are shown in the figure.

According to sommerfeld each

momentum component is
separately quantized as

 P dr = n h
r r

 P d = n h
Where, Pr andP are the
components of linear
momentum P of the electron along radial direction and transverse direction. nr andn are the
integers, and indicates that the integration is to be carried over one period of the motion.
SOMMERFELD RELATIVISTIC CORRECTION:
The velocity of the electron moving in an elliptical orbit varies at different parts of the
orbit. The velocity is maximum when the electron is nearest to the nucleus and minimum when it
is farthest from the nucleus. Therefore the effective mass of the electron will be different at
different parts of its orbit. Hence the curvature of elliptical path is not exactly the same in two

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positions and hence the ellipse is not complete one. Sommerfield has shown that the path of the
electron is not closed ellipse but a complicated curve known as rosette-a processing ellipse as
shown in the fig.
In an elliptical orbit, the velocity of the electron becomes very large when it passes
close to the nucleus. Now its mass also increases. This effect makes the energy of the electron in
an elliptical orbit greater than in a less elliptical orbit. Hence the different n orbits with a given
n have slightly different energies.

The energy of an electron in a particular state

characterized by quantum number n and n , after relativistic
corrections can be written as
  
 2 2  
mz e   z  1
2 4
3 
En = − 1+ −
8 0 c 2 h 2  n  n 4n  
2

  
   
2
e 1
Where  = 
z 0 ch 317
 is called sommerfeld’s fine structure constant.
From the above equation it is clear that the energy of an electron depends not only on the
principal quantum number.
For n=1, n =1 only one energy level exist
For n=2, n =1, 2 only two energy level exist.
For n=3, n =1, 2, 3 only three energy level exist
Here the energy difference between these levels is very small and the frequency of
radiation emitted in the transition of electron from n = 3 to n = 1 will be slightly different. This is
the reason why a single line of hydrogen spectrum should appear as a group or closely associated
lines.
VECTOR ATOM MODEL
DRAWBACKS OF BOHR AND SOMMERFELD ATOMIC MODEL
(1) Bohr’s theory was in capable of explaining the fine structure of the spectral line.
(2) In the case of complex atoms, Bhor’s theory fails to calculate the energy of the system
frequencies of radiation emitted.
(3) Sommerfeld modification was not predicting the correct number of observed fine
structure of hydrogen.
(4) Both models could not explain the distribution and arrangement of electrons in atoms.
(5) Both models could not explain the variation of intensities in the spectral line.
(6) Both models could not explain both stark and Zeeman Effect.
CONCEPT OF VECTOR ATOM MODEL:
This model explains the concept of spacial quantization and spinning electron.
(1) Space quantization:

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 According to Bhor’s theory, the moving electron in a circular orbit has only one degree of
freedom. According to sommerfield’s elliptical orbits, the electron possess two degrees of
freedom, one due to nr and the other due to n .
In general the motion of electrons in an atom is three dimensional and possesses three
degrees of freedom. Hence an additional quantum number is required to describe the state of
electron in the atom in which the orbits are assumed to be quantized both in magnitude and
direction. The orientation of elliptical orbit in three dimensions does not alter the original
sommerfeld orbit. Thus the introduction of spacial quantization makes the orbit vector quantized.
According to the rule of space quantization, the electron orbit can only set itself in certain
discrete positions with respect to the field direction only. This is known as spacial quantization
and was proposed by sommerfeld.
SPINNING OF ELECTRONS:
To explain many lines consist of a group of lines closed to each other Uhlenback and
Goudsmit proposed the hypothesis of electron spin. According to this hypothesis, the electron
revolves not only in an orbit but also about its own axis. Hence electron has orbital motion and
spin motion. According to quantum theory, the spin motion should be quantized. Hence a new
quantum number called as spin quantum number is introduced. The orbital and spin motions are
considered as quantized vectors and hence the atom model is known as vector atom model.
STERN-GERLACK EXPERIMENT:
In Stern-gerlack experiment a beam of silver atoms is produced from an electric oven and
passed the beam through slits s1 and s2

This type of silver atom is passed through an inhomogeneous magnetic field as shown in
the fig. The magnetic field is of much greater intensity near the knife edge than any where else in
the gap. A photo graphic plate records the configuration of the beam. The whole arrangement is
enclosed in a highly evacuated glass vessel.
In the absence of magnetic field, we get a photograph of a narrow strip. In the presence of
the inhomogeneous magnetic field the strip splits up into two components as shown in the fig (b)
as a result of electron spin.

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 Fig. b

EXPLANATION:
Atomic number of Ag is 47.According to Pauli’s exclusion principle all the inner shells
and sub shells are completely filled except the outermost electron in 5s state. Thus Ag is
monovalent element. So 5s electron is responsible for the magnetic moment of the atom. When
all silver atoms possessing a magnetic moment  J pass through the inhomogeneous magnetic
field, they experience different amount of force in vertical direction depending upon their
orientation. If the magnetic moment  J can have all possible orientations, then the beam of
silver atoms will be spread out into a broad continuous band on emerging from the magnetic
field. But experimentally only two narrow strips are obtained on the photographic plate.
Therefore the predictions of classical physics are not correct. According to quantization rules

j ( j + 1).
h
Angular momentum J =
2
There are 2j+1 possible orientations of J
The Stern-gerlack experiment shows that 2j+1 = 2 or j = 1/2
3 h
Thus J = .
2 2
We know that the angular momentum J of silver atoms is entirely due to spin of its
valence electrons. Hence we conclude that the electron has a spin angular momentum
S = s (s + 1).
h
. Where s = 1/2
2
Hence Stern and Gerlach found that the initial beam split into two distinct parts
corresponding to two opposite spins.
AN EXPRESSION FOR THE AMOUNT OF DEVIATION PRODUCED:
As shown in the fig non-uniform magnetic field is taken along y-axis .The field gradient dB/dy is
+ve. Let the atomic magnet with magnetic moment M, pole strength P and length l inclined at an
angle  with the field direction. If the field strength at one pole is B then the pole strength at
 dB 
other pole will be B +  l cos 
 dy 

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 The extra force Fy is given by

dB dB
Fy = pl cos  . = M cos  . − − − − − − − −(1)
dy dy
Due to this force the atomic magnet will be displaced from its straight path in the field direction.
Let the silver atoms enters the non-uniform magnetic field with velocity v and the length
of the path be L for which time taken is t. The displacement along the field direction is given by
1
d y =  yt 2
2
Here  y is the acceleration of the atom along field direction.
Fy
y = m=mass of the atomic magnet.
m
2
1 Fy 1 Fy  L 
dy = . t2 = .  
2 m 2 m v
1 M cos  dB  L 
2

dy = . . .  − − − − − − − − − (3)
2 m dy  v 
From the above equation we can calculate the displacement of the atom along the field direction.
QUANTUM NUMBERS ASSOCIATED WITH VECTOR ATOM MODEL:
The quantum numbers associated with each of the electron in a given atom are
(1) THE PRINCIPAL QUANTUM NUMBER (n): n = 1, 2, 3……
It tells about the energy of an electron and the size of the orbital i.e., the distance from the
nucleus. The principal quantum number n is a +ve integer.
The energy of the electron is given by
En = -13.6/n2 ev
The distance from the nucleus for Hydrogen atom is given by
rn = 0.529n2 A0
The principal quantum number n=1,2,3,4… are denoted by K,L,M,N,O,P,Q…The number of
electrons in a shell is limited to 2n2. The total number of orbitals for a given n value is n2. For a
hydrogen atom with n=1, the electron is in its ground state. If the electron is in the n=2 orbital it
is in excited state.
(2) ORBITAL QUANTUM NUMBER (l): l = 0, 1, 2, 3, .., n-1

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 This quantum number defines the shape of the orbital occupied by the electron and the
orbital angular momentum of the electron. The secondary quantum number divides the shells
into smaller groups of orbitals called sub shells. The orbitals corresponding to l=0, 1, 2, 3… are
denoted as s(sharp), p(principal), d(diffuse), f(fundamental)…
If n=1, l=0 there is only one possible orbital(s-orbital)
n=2, l=0, 1 there are two possible orbitals(s, p)
n=3, l=0, 1, 2 there are three possible orbitals(s, p, d)
h
The orbital angular momentum Pl = l (l + 1).
2
The orbital quantum number l is similar to the azimuthal quantum number np of sommerfield
theory. The two are related by l= (n − 1)

(3) SPIN QUANTUM NUMBER (s):

Spin quantum number specifies the orientation of the spin axis of an electron. The
magnitude is always half. Since, the electron can spin clockwise or anti clockwise, there are two
values 1/2,-1/2 depending upon clock wise or anti clockwise. The angular momentum Ps is given
by Ps = s (s + 1).
h
2
(4) TOTAL ANGULAR MOMENTUM (j):
This quantum number represents the resultant angular momentum of the electron due to
both orbital and spin motions. This can be expressed as j= (l+1/2).plus sign is used when s is
parallel to l and minus when s is anti-parallel to l. the total angular momentum of the electron is
h
Pj = j.
2
(5) MAGNETIC ORBITAL QUANTUM NUMBER (ml):
We know that due to space (direction) quantization, the orbital angular momentum can
have orientations in space such that its projection on a fixed direction can vary from –l to +l in
steps of one unit. This projection of l in the field direction is known as magnetic quantum
number. ml= l, (l-1), (l-2),…1, 0, -1,.., (l-2), (l-1), -l

In the above figure the different

values of ml = (-3,-2,-1,0,1,2,3)are shown
for l=3. There are (2l+1) allowed
orientations of the ml vector.
(6) MAGNETIC SPIN QUANTUM
NUMBER (ms):
In an external magnetic field, the
spin angular momentum Ps can have only two possible orientations for which the projections will
be having values ms = -1/2 and ms=+1/2. ms can be either +1/2 or -1/2 and has no other values for
a single electron
(7) MAGNETIC TOTAL ANGULAR MOMENTUM QUANTUM NUMBER (mj):

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 Its numerical values are the projection of the total angular momentum vector j on the
field direction. Since j can have half integral values, mj can also assume half integral values. The
possible values of mj are –j, (-j+1)…,1/2, 3/2, 5/2.,…,(j-1), j excluding zero for single electron.
The permitted orientations of j are (2j+1) and hence mj can have only (2j+1) values from
+j to -j excluding zero. This explains the splitting of spectral lines in a strong magnetic field.
COUPLING SCHEMES:
When we consider a number of electrons, the total angular momentum would depend
upon the coupling (interactions) between orbital and spin angular momenta. Generally two types
of coupling known as Russell-Saunders or L-s coupling and j-j coupling occurs.
(1) L-S COUPLING: In this coupling all the orbital angular momentum l of the electrons
combine to form a resultant vector L and all the spin angular
momentum vectors s combine to form a resultant vector S. now
the vector Land S combine to form a vector J which represents the
total angular momentum of the atom. This can be represented as
L= (l1+l2+…)
S= (s1+s2+s3…)
J=L+S

Here L is always an integer i.e., 0, 1, 2, 3…. the value of S

depends upon the number of electrons and direction of their spin
vector. In the case of two electrons, the value of s is one or zero.
In the case three electrons, the value of S may be 3/2 or 1/2 . In
the case four electrons the value of S may be 2, 1 or zero. Thus S
is an integer for an even number of electrons and half integer for
an odd number of electrons.
Now J=0, 1, 2, 3….. When S is integer
J=1/2, 3/2, 5/2…when S is half integer
J must always be +ve and never –ve.
(2) J-J COUPLING:

In j-j coupling, each electron is considered separately and its total

angular momentum j is obtained by the relation j=l+s. then the total
angular momentum J of the atom would be vector sum of all the
individual j vectors of the electrons.
Hence j1= (l1+s1), j2= (l2+s2), j3= (l3+s3)….
J=j1+j2+j3+….
J=  j
In most of the known cases L-S coupling is effective.

Spectral terms and spectral notations:

Spectral terms : A quantity used in spectroscopy, which is proportional to the steady-state
energy of an atom or molecule. Spectral terms were first introduced empirically in the analysis
of regularities of the positions of lines in spectra.

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Example: The spectral terms are location of a state of the atom or electron of physical system

and there are rules for writing the terms.

For example if an electron is in a state defined by a j value where j= l +s

One can write (2s +1) T (j) ….it signifies the degeneracy of spin state i.e. 2s+1

if l=1 then T=P

if l=0 T=S state

if l=2 D state

spectral notations: The atomic level is described as n 2S+1LJ where S, n, and J are the quantum
numbers defined above, and L is the term (S,P,D,F,G, etc). 2S+1 is the multiplicity. n
lx 2S+1LJ where l is the orbital of electron (s, p, d, etc.) The outermost electron in an atom or ion is
the one that usually undergoes transitions, and so the state of that electron describes the state of
the atom or ion.

The configuration describes the n and l values for all the electrons in an atom. For example, the
ground state of Boron has a 1s22s22p configuration, with 2 electrons filling the n=1 level (l=0), 2
electrons in the n=2, l=0 s orbital, and the fifth electron beginning to populate the 2p orbital.

The level is the set of 2J+1 states with specific values of L, S, and J. The difference in the energy
between two levels gives the wavelength or frequency of an atomic transition.

The term is the set of levels characterized by a specific S and L. The ground state of Boron has
a 2P1/2 term. Closed shells always have a 1S0 term.

Atoms whose outer electrons have l=0,1,2,3,4 are referred to as S, P, D, F, G terms,respectively .

Selection Rules: In complex ions, there are an enormous number of possible transitions. Not all
of these possible transitions are observed. This is because some transitions are more likely than
others. Selection rules were arrived at empirically to describe those changes in quantum numbers
that were observed and those which did not (forbidden transitions). The basic selection rules,
which strictly apply only to simple configurations which obey strict L-S coupling are:

• ΔL = 0, +/- 1
• Δl = 1
• ΔJ = 0, +/- 1, except that J=0 -> J=0 is forbidden.
• ΔS = 0
• ΔM = 0, +/- 1, except that M=0 -> J=0 is forbidden if ΔJ=0.

As the atoms become more complex, strict L-S coupling fails to hold, and these selection effects
become weaker.

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Permitted lines are those whose transition probability is high, i.e., whose Einstein A value is
small, of order 108s-1. Forbidden lines have small AUL values, of order 1, because they cannot
radiate in a dipole transition. Forbidden transitions are often possible through quadrupole or
octopole transitions, which have low transition probabilities. Metastable lines have intermediate
A values. A-1 gives the radiative lifetime of the excited state. Forbidden lines are characteristic of
low density media, because at high densities the time between collision is short compared to the
radiative lifetime, so collisional deexcitation is the dominant process.

Intensity rules: The intensity of spectral lines is determined by the relative probabilities
transitions between various energy levels. Selection rules for rotational Raman allow only
J= 2. The intrinsic probability for a transition of a single molecule from J = 0 to J = 2 is the same
as that for a transition from J = 1 to J = 3.
ZEEMAN EFFECT:
In 1986 Prof. Zeeman discovered that when a source of radiation, giving line spectrum is
placed in a magnetic field; the spectral lines are split up into a number of component lines,
symmetrically distributed about the original line. This is known as Zeeman Effect.
If the magnetic field is very strong, each spectral line is split up into two components in
the longitudinal view and three components in transverse view. This is normal Zeeman Effect.
When the magnetic field is weak, each line splits into more than three components. This is
known as Anomalous Zeeman Effect.

EXPERIMENTAL ARRANGEMENT:

The experimental arrangement is as shown in

the figure. The source of radiation such as sodium or
mercury arc is placed between the pole pieces of a
powerful electromagnet. It is in conical shape and holes
are drilled along the length so that the light from the
source can pass through it. Hence the spectrum can be
observed along the direction of magnetic field. The
spectral lines are observed with a high resolving power
spectroscope. The spectral lines may also be observed in a direction perpendicular to the
magnetic field.
In the normal Zeeman Effect, when the light is observed perpendicular to the direction of
magnetic field, three components are observed. One in the same position having frequency  and
two components being on either side of the central line  +  and  −  . When the light is
observed along the direction of magnetic field the same two additional lines with frequencies
 +  and  −  are observed while the central line is missing.

APPLICATION OF ZEEMAN EFFECT:

Using Zeeman Effect the specific charge e/mo of the

electron can be calculated. When the source is placed in the

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magnetic field, the change in frequency d  of the spectral line is given by
eB
d =
4mo
−c
c
If  be the wavelength, then  =
, d =  2  d
  
2
 eB
2
eB 2
d  = d = . =
c c 4mo 4mo c
e 4c d
 = .
mo Bn 2

MOLECULAR SPECROSCOPY
INTRODUCTION:
When electromagnetic radiation is allowed to fall on an atomic system, the electrons of
that atom absorb the photon energy of incident radiation and goes to excited state. After the life
time is completed the atoms come to the excited state by emitting the energy equal to the energy
difference of the two states. The emitted photon is also having a single wavelength or frequency
and the spectrum is known as line spectra or atomic spectra.
MOLECULAR SPECTRA:
This spectroscopy deals with the interaction of electromagnetic radiation with molecules. The
molecule is also having ground state and excited states. If the incident radiation on molecule is
less than the energy difference of ground state and excited state, then the molecule rotates about
its centre of mass giving rise to rotational energy levels. If the incident radiation is having still
more energy than the above case, the nuclei of molecule vibrate along the inter-nuclear axis
giving rise to vibrational energy levels. The electronic transition in molecule takes place in the
ultra violet or visible region of the electromagnetic spectrum. Etotal = Erot + Evib + Eele
RAMAN EFFECT:
When monochromatic beam of light of frequency  o is passed through a dust free

transparent substance the light is scattered in all directions. Most of the scattered radiation has
the frequency  o as that of incident radiation. This was observed by Raman in 1928 and the

effect is known as Raman Effect.

If  i and s are the frequencies of the incident and scattered radiation the difference in
frequency  =  i −  s is known as Raman shift. The Raman spectra of ccl4 are shown in the fig.

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 The lines on the lower frequency side are called stokes lines and those on higher
frequency side are known as anti-stokes lines of unchanged frequency are due to Rayleigh
scattering stokes lines are always more intense than anti-stokes lines.
CHARACTERISTICS OF RAMAN EFFECT:
(1) The frequencies of Raman lines depend on the frequency of incident light.
(2) The displacement of Raman lines from the original line depend on the nature of scattering
substance.
(3) The anti stokes lines are weaker than stokes-lines.
(4) Raman Effect is purely a molecular phenomenon.
(5) The rotational or vibrational state of the molecule is changed due to scattering of light by
it.
EXPERIMENTAL ARRANGEMENTS FOR RAMAN SPECTROSCOPY:

In Raman spectrometer the sample is irradiated with mono-chromatic light and is

observed at right angles to the incident radiation. The experimental arrangement is as shown in
the fig. it consists of the following parts.
(1) source (2) Raman tube (3) spectrograph
Raman tube C is filled with the liquid which is to be investigated. It is made of glass and is 1-2
cm in diameter and 10-25 cm long. One end of the tube is drawn like a horn and blackened
outside to provide a suitable black background. The other end of the tube is closed with an
optically plane glass plate. The scattered light emerges through the window W. the Raman tube
is surrounded by water to cool the sample.
S is a mercury arc lamp which acts as a source of light. This light is filtered by nickel
oxide glass filter to get a mono-chromatic the light is then allowed to pass through an opening in
a metallic reflector which then falls on Raman tube. The experimental sample is placed inside the
Raman tube. The scattered beam emerges from the flat end of Raman tube and is examined by
means of a spectrograph.
When the sample is a gas, it is enclosed in a tube at a pressure of a few cm of Hg.
In the case of solids, powders are used. They are mixed either with liquid paraffin or any other
solvent.

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QUANTUM THEORY OF RAMAN EFFECT: According to quantum theory, the incident
radiation of frequency  can be treated as consisting of a stream of particle called photons
having energy h .Interaction of incident radiation with molecules of the transparent substance
can be treated as collision between photons and molecules of the substance.
Suppose a molecule of mass m in the energy state Ep is moving with velocity v and is colliding
with a light photon of energy h . Suppose this molecule undergoes a change in its energy state
as well as in its velocity. Let this new energy state be Eq and the velocity is V ̍. From the
principle of conservation of energy, we have
1 1
E p + mV 2 + h = E q + m(V ) 2 + h 
2 2
Since the change in velocity of the molecule is negligible the above equation can be written as
E p + h = E q + h 
E p − Eq
or   =  +
h
or   =  + 
From this equation three different situations can occur. They are
1) If Ep = Eq, then   =  and this refers to unmodified line where the molecule simply deflects
the photon without receiving energy from it.
2) If Ep > Eq, then     and this refers to anti-stokes lines. Here the molecule was previously
in the excited state and it handed over some of its intrinsic energy to the incident photon. Hence
the photon has greater energy.
3) If Ep < Eq, then     and this
refers to stokes lines. Here the
molecule absorbed some energy
from the photon. Hence the photon
has lower energy.
The three different situations are
shown in the following figure.

For transition between the energy

levels, we get different spectral
lines.
APPLICATIONS OF RAMAN EFFECT:
(1) To study the structure of crystal and compounds.
(2) To know the number of atoms in a molecule, their relational arrangement, relative mass
and chemical bonds between them.
(3) To study the composition in plastic, mixtures etc.
(4) To decide about single, double, triple bonds.
(5) To study the spin and statistics of nuclei.
(6) To study the binding forces between the atoms or groups of atoms in crystals.
(7) The study the rotational or vibrational energy levels of homo nuclear molecules as
example nitrogen, oxygen etc...
(8) To determine many of the structural parameters of the molecule.

GMS-14
 UNIT II
MATTER WAVES &UNCERTAINTY PRINCIPLE
SYLLABUS: Matter waves, de Broglie’s hypothesis, Wave length of matter waves,
Properties of matter waves, Davisson and Germer’s experiment, Phase and group velocities,
Heisenberg’s uncertainty principle for position and momentum& energy and time,
Illustration of uncertainty principle using diffraction of beam of electrons (Diffraction by a
single slit)and photons(Gamma ray microscope),Bohr’s principle of complementarity.

MATTER WAVES
INTRODUCTION:
The particle is specified by (1) mass (2) velocity (3) momentum (4) energy. A wave is
specified by its (1) frequency (2) wavelength (3) phase of wave velocity (4) amplitude (5)
intensity. Radiation has a dual mature i.e., radiation is a wave which is spread out over space and
also a particle which is localized at a point in space. Radiation sometimes behaves as a wave and
at other times as a particle.
DE BROGLIE’S HYPOTHESIS OF MATTERWAVES:
DE-BROGLIE in 1924 suggested that the correspondence between wave and particle
should not confined to electromagnetic radiation, but it should also be valid for material
particles. Like radiation, matter also has a dual nature. A moving particle is controlled by the
wave in a manner similar to that in which a photon is controlled by waves.
According to DE-BROGLIE’S hypothesis, a moving particle is associated with a wave
which is known as DE-BROGLIE wave. The wave length of the matter wave is given by
h h
= =
mv p
PROPERTIES OF MATTER WAVES:

1) If the particle is lighter, then the wavelength associated with it is greater.

2) If the velocity of the particle is smaller, then the wavelength associated with it is
greater.
3) When V=0, then λ = ∞
When V=∞, then λ = 0
This shows that matter waves are generated by the motion of particles. These waves are
produced whether the particles are charged particles or they are uncharged. This fact reveals that
these waves are not electromagnetic waves but they are new kind of waves.
4) The velocity of matter waves depends on the velocity of matter particle.
5) The velocity of matter waves is greater than the velocity of light.
6) Waves have particle-like properties and particles have wave-like properties.
7) The wave nature of matter introduces an uncertainty in the location of the position of the
particle.

GMS-15
EXPRESSION FOR DE-BROGLIE’S WAVELENGTH:
According to Planck’s theory of radiation the energy of a photon is given by
hc
E= h = − − − − − − − − − −(1)

According to Einstein’s mass energy relation
E=mc2--------------------------- (2)
hc hc h h
From esq. (1) and (2) we get mc 2 = or = = =
 mc 2
mc p
Here p=mc, momentum associated with photon
If we consider a material particle of mass m moving with a velocity v then the
h h
wavelength associated with this particle can be expressed as  = =
mv p
SPECIAL CASES:
1 p2
(1)If E is the K.E of the material particle then E = mv 2 = => p = 2 Em
2 2m
h
DE-BROGLIE wavelength  =
2 Em

(2) When a charge particle carrying a charge q is accelerated by a potential difference V then its
K.E is given by E = Vq
h
 =
2mqV
3
(3) When a material particle is in equilibrium at a temperature T then E = KT
2
h h
= =
3  3mKT
2m KT 
2 
VELOCITY OF DE-BROGLIE’S WAVES:
h
DE-BROGLIE’S wavelength  = − − − − − − − − − (1)
mv
Velocity of DE-BROGLIE’S wave V =  − − − − − −( 2)
The energy of the particle is E = h ---------------------- (3)
From relativity E=mc2------------------------------------- (4)
mc 2
 h = mc =  =
2

h
mc 2 mc 2 c2
From eqns. (1) and (2) we get V = . = . =
h mv v
THE CONCEPT OF PHASE AND GROUP VELOCITIES:
WAVE VELOCITY:

GMS-16
When a mono chromatic wave travels through a
medium, its velocity in the medium is called as waver
velocity. Consider a wave whose displacement is
Y=a sin (t − Kx)
Here k is known as propagation constant.
The ratio of angular frequency  to the propagation
constant K is defined as wave velocity V p .

V p =
K
For the wave (t − Kx) is the phase of wave motion
For the planes of constant phase (t − Kx) =constant
dx dx 
Differentiating the above eq. with respect to t we get  − K = 0 => = = Vp
dt dt K
Thus the wave velocity is the velocity with which the planes of constant phase advance
through the medium. Due to this reason, the wave velocity is also known as phase velocity.
GROUP VELOCITY:
When we consider a pulse it consists of a number of waves slightly differing in frequency
from one another. The superposition of such waves is known as wave group (wave packet).
When such a group travels in the medium, the phase velocities of different components are
different. The observed velocity is the velocity with which the maximum amplitude of the group
advances. This is called group velocity. Hence group velocity with which the energy in the group
d
is transmitted. Group velocity V g =
dK
PHASE VELOCITY AND GROUP VELOCITY FOR DE-BROGLIE WAVES:
h
The DE-BROGLIE wave  =
mv
 = 2,
mc 2
But E = h = mc 2 =  =
h

2mc 2
 =
h
mo
Also we know that m =
v2
1−
c2
2mo c 2
 = − − − − − − − − − − − − − − − − − − − −(1)
v2
h 1− 2
c

GMS-17
 2 2mv 2mo v h
K= = = − − − − − − − − − − − − − −( 2)   =
 h v2 mv
h 1− 2
c
 c2
The phase velocity of DE-BROGLIE is given by VP= = − − − − − −(3)
K v
d d / dv
The group velocity of DE-BROGLIE is given by Vg= = − − − − − (4)
dK dK / dv
d 2mo v
From eq. (1) we have = 3
− − − − − − − − − − − − − − − − − − − − − −(5)
dv v2 2
h(1 − 2 )
c
dK 2mo
From eq. (2) we have = 3
− − − (6) Vg =  − − − − − − − − − − − − − −(7)
dv v2 2
h(1 − 2 )
c
The DE-BROGLIE wave group associated with a moving particle travels with the same velocity
as that of the particle.
ELECTRON DIFFRACTION EXPERIMENT BY DAVISSION AND GERMER:
In 1927 two American physicists, Davisson and Germer succeeded in measuring the DE-
BROGLIE wavelength associated with slow electrons. The experimental arrangement is as
shown in the fig.

The apparatus consists of an electron gun G where the electrons are produced and obtained in a
fine pencil of electronic beam of known velocity. The electron consists of a tungsten filament F
heated to dull red. Electrons are emitted from the filament due to thermionic emission. The
electrons are collimated by suitable slits to obtain a fine beam. The beam of electrons is directed
to fall on a large single crystal of nickel. This is known as target T. the electrons are diffracted in
different directions like a wave. The angular distribution is measured by an electron detector
which is connected to a galvanometer. The faraday cylinder can move on a circular scale S
between 29o to 90o to receive the reflected electrons. A retarding potential is m reflected

GMS-18
electrons. A retarding potential is maintained between two walls of faraday cylinder. Hence it
receives only fast moving from the electron gun. The secondary electrons produced by collisions
with atoms from nickel target are reflected by faraday cylinder. Hence the galvanometer
deflection is only due to electrons from electron gun.
EXPERIMENTAL PROCEDURE:
Let us consider the beam of electrons is incident normally on the crystal surface. The
surface layer of the crystal acts as a diffraction grating.
For each azimuth, a beam of low voltage electrons is made to fall normally on the crystal
surface. The collector is moved to various positions along the circular scale S. At each position
the deflection in the galvanometer is noted. This deflection is a measure of the intensity of the
scattered electrons. A graph is then plotted between galvanometer current against angle 
between incident beam and the beam entering the cylinder. The experiment is repeated for
several accelerating voltages V. this is shown in the fig (2)

It is observed that a bump begins to appear in the curve for 44 volt. The following points are
observed.
(1) If the potential is increased then the bump is moved upward.
(2) The bump becomes most prominent in the curve for 54V at  = 50 0
(3) At higher potentials the bump gradually dis-appears.
According to DE-BROGLIE wavelength associated with electrons accelerated through a
potential V is given by

GMS-19
 12.26 0
= A
V
12.26
Here wavelength associated with 54V electrons is  = = 1.67 A 0
54
From X-ray analysis, it is known that a nickel crystal acts as plane diffraction grating with
grating space d = 0.91A0. According to experiment, the wavelength of the electron beam is  =
2d sin ѳ̍ = 2(0.91) sin 65◦= 1.65 A◦. This is in good agreement with the wavelength calculated
from the DE-BROGLIE hypothesis. Hence confirms the DE-BROGLIE concept of matter
waves.
DOUBLE SLIT EXPERIMENT:

This experiment proves the interference of electron waves just like photons. The
experimental arrangement is as shown in the fig.
In the fig electron gun contains a filament FF and a cylindrical anode AA. electron gun
supplies a mono energetic beam passes through a narrow slit SS. two slits S1 and S2 very close to
each other is placed in the path of electron beam. PP is a photographic plate. The whole chamber
is evacuated.
The electron beam is diffracted by slits S1 and S2 which acts as coherent sources. Hence
the diffracted beams of electrons interfere and produce interference pattern on photo graphic
plate. The interference pattern shows the existence of waves associated with electrons.
Knowing the separation between S1 and S2 and their distance from photographic plate,
the wave length of the electron beam can be calculated. This is equal to the wavelength obtained
by DE-BROGLIE relation. This proves the existence of matter waves associated with material
particles.

GMS-20
STANDING DE-BROGLIE WAVES OF ELECTRON IN BOHR ORBITS:
According to DE-BROGLIE hypothesis, an electron of mass m in motion with velocity v
h
is associated with a wave whose wavelength  is given by  = ----- (1)
mv
According to Bhor electron does not radiate energy while moving in an orbit. The wave
associated with electron must be stationary wave and also there should be no transfer of energy.
DE-BROGLIE on the basis of his hypothesis proposed an atomic model in which
stationary orbits of the Bhor’s model were retained but with the difference that electron in
various orbits behaves as wave. This is shown in the fig.

He suggested that stationary orbits are those in which orbital circumference (2 r ) is an integral
multiple of DE-BROGLIE wavelength  . 2r = n where n=1, 2…
h h
But  = angular momentum of electron L=m v r =n. --------- (2)
mv 2
Esq. (2) is nothing but the Bhor’s postulate i.e., the total angular momentum of the moving
h
electron is an integral multiple of . Thus the new concept of DE-BROGLIE confirms Bhor’s
2
postulate.

UNCERTAINTY PRINCIPLE:
CONSEQUENCES OF DE-BROGLIE CONCEPT:
(1) The wave properties associated with electrons are utilized to design electron microscope. It
has 1000 times better resolution than optical microscope.
(2) De-Broglie explained the quantization of angular momentum in terms of wave nature of
moving electron around the nucleus.
(3) The neutron diffraction is a quite common technique for investigation of the structure of
matter.
(4) De-Broglie concept of matter waves leads to Bhor’s principle of complimentary which states
that the two apparently different views of wave and particle.

GMS-21
(5)De-Broglie concept leads to un-certainty principle. The material particle exhibits particle
nature as well as wave nature. But the two natures can’t be exhibited simultaneously. This leads
to un-certainty principle.
HEISENBERG UNCERTAINTY PRINCIPLE:
According to him “it is impossible to measure both position and momentum of a particle
simultaneously to any desired degree of accuracy.” Qualitatively this principle states that “the
order of magnitude of the uncertainties in the knowledge of two variables must be at least
Planck’s constant h.
Considering the pair of physical variables as position and momentum, we have
px  h − − − − − − − − − − − − − − − (1)
where,  p is the uncertainty in determining the momentum and x is the uncertainty in
determining the position of the particle. Similarly we have
Et  h − − − − − − − − − − − − − − − − − (2)
J  h − − − − − − − − − − − − − − − − − (3)
Where E and t are un-certainties in determining the energy and time. While J and  are
uncertainties in determining angular momentum and angle.
PRINCIPLE:
The product of un-certainties in determining the energy and momentum of the particle
h
can never be smaller than the order of . So we have
4
h
px 
4
h
Et 
4
h
J 
4
TIME ENERGY UNCERTAINTY PRINCIPLE:
Let us consider the case of a free particle with rest mass mo moving along x-direction
with velocity Vx.
2
1 Px
The kinetic energy E = mo v x = − − − − − − − − − − − (1)
2

2 2mo
If Px and E be the uncertainties in momentum and energy, then differentiating eq. (1) we get
2 Px Px
E =  Px Px = mo E
2mo
mo 1
 Px = E  Px = E − − − − − − − − − − − − − ( 2)
Px Vx
Let the un-certainty in time interval for measurement at point x be t , then uncertainty x in
position is

GMS-22
x = Vx t − − − − − − − − − − − − − − − − − −(3)

x
Vx =
t
By substituting the value of Vx in eq. (2) we get
t
Px = E  xPx = tE − − − − − − − −(4)
x
h h
We know that xPx   tE  − − − − − − − − − − − − − − − (5)
4 4
Hence the product of un-certainty in energy and un-certainty in time can never be smaller than
h
.
4
From esq. (5) it is clear that the system that remains in a certain state for a very long time
can have a very well defined energy. But shorter the time of stay, larger will be uncertainty in
corresponding energy. An atom can live in the exited state only for about 10-8 s. Thus the
concept of Bhor’s orbits violates the un-certainty principle.
CONSEQUENCES OF UN-CERTAINTY RELATION:
(1) DETERMINATION OF THE POSITION OF A PARTICLE BY GAMMA RAY
MICROSCOPE:

Let us measure the position of the particle in the field of gamma ray microscope. The
least distance between two close points that can be resolved by the microscope is given by

x  − − − − − − − − − − − − − (1)
2 sin 
Where  is the wavelength of the light used, and  is the semi-vertical angle of the cone of the
light and x is the un-certainty in determining the position of the particle.
In order to observe the electron, it is necessary that at least one photon must strike the
h
electron and scatter inside the microscope. When the photon of initial momentum P= . After

scattering enters the field of view of microscope, it may be anywhere with an angle 2 . Thus its
x component of momentum Px may lie between P sin  and − P sin  . Since the momentum is

GMS-23
conserved during the collision, the un-certainty in the measurement of the x component of the
momentum is
Px = P sin  − (− P sin  ) = 2 p sin  − − − − − − − − − − − − − (2)
2h
Px = sin 

From eq. (1) and eq. (2) we have
 2h
xPx  . sin 
2 sin  
xPx  h − − − − − − − − − − − − − − − − − (3)
From the above equation it is clear that the product of un-certainties in position and momentum
is of the order of Planck’s constant.
(2) DIFFRACTION BY A SINGLE SLIT:

As shown in the fig, suppose a narrow beam of electron passes through the single narrow
slit and produces a diffraction pattern on the screen. The first minimum of the pattern is obtained
by putting n=1 in the equation d sin  = n
 y sin  =  − − − − − − − − − − − − − (1)
Here  y is the width of the slit and  is the angle of deviation corresponding to first minimum.
In producing diffraction pattern on the screen all the electrons have passed through the
slit. But we cannot say definitely at what place of the slit. Hence the un-certainty in determining
the position is equal to the width  y of the slit.

 y = − − − − − − − − − − − − − −(2)
2 sin 
After diffraction at the slit the electrons deviated from their initial path. Hence un-
certainty in Y-component of momentum is
h
Py = 2 P sin  = 2 sin  − − − − − − − − − − − − − (3)

(2) POSITION OF ELECTRON IN BOHR ORBIT:
In calculating the radius of Bhor’s first orbit: If x and P are the uncertainties in position
and momentum of the electron in the first orbit, then according to uncertainty principle we have,

GMS-24
 h
x.P 
4
h
P  − − − − − − − − − − − − − − − (1)
4x
The uncertainty in K.E. , T of the electron may be written as
m 2 (v ) (P )2
2
T = m(v ) 
1

2

2 2m 2m
2
h
T  − − − − − − − − − − − − − − − −(2)
16 2m(x )
2 2

The un-certainty in the potential energy V of the same of the electron is given by
− 2e 2
V  − − − − − − − − − − − − − − − − − −(3)
x
The un-certainty in total energy E is given by
h2 − 2e 2
E  T + V  + − − − − − − − − − − − − − (4)
16 2 2m(x ) x
2

The un-certainty in the energy will be minimum if

d (E ) d 2 (E )
= 0 and 2 is positive.
d (x ) d (x )
d (E ) − 2h 2 2e 2
Now  + =0
d (x ) 16 2 2m(x )3 (x )2
h2 2e 2 h2
   x  − − − − − − − − − − − − − − − −(5)
16 2 m(x ) (x )2 16 2 m2e 2
3

From esq. (2) and eq (3) we have

 2h sin 
y.Py  . h
2 sin  
y.Py  h − − − − − − − − − − − − − − − − − −(6)
This relation shows that the product of un-certainties in position and momentum is of the
order of Planck’s constant.
CONSEQUENCES OF UN-CERTAINTY RELATION:
(i) Particle in the box: consider a particle of mass m moving in one-dimensional box of length L
in X-direction as shown in the fig. the minimum un-certainty in the position x of the particle will
be x = L . Hence L is the width of the box.

GMS-25
  
According to un-certainty principle x.P    P  
x L
h
Approximately, the above equation can be written as P  P 
2L
P2 h2  2 2
Energy E=  E
2m 8mL2 2mL2
d 2 (E )
If we calculate the value of it becomes positive and hence x given by the equation (5)
d (x )
2

is minimum. This shows that the energy of the electron is minimum in the first orbit. Hence the
radius of the first orbit is given by
h2
r  x 
16 2 mze2 Where  =
h
 2
2
r 2
4mze
COMPLEMENYTARY PRINCIPLE OF BOHR:
The most important consequences of un-certainty principle are it is impossible to determine the
wave and particle properties at the same time in a single experiment.
According to complementary principle, the wave and the particle nature of matter and
light complementary rather than contradictory.
Let us consider an experimental arrangement in which light is diffracted by a double slit and is
detected on a screen that consists of many adjacent photo-electric cells. The photo electric cells
respond to photons. If we plot the no: of photons, against the location of cell, a wave like pattern
is obtained. It follows that any experiment which can be devised displays either the particle like
characteristics or wave-like characteristics of the system. The wave and the particle pictures give
complementary description of the same system.

GMS-26
 UNIT-III:
QUANTUM (WAVE) MECHANICS
SYLLABUS:Basic postulates of quantum mechanics, Schrodinger time independent and time
dependent wave equations-Derivations, Physical interpretation of wave function, Eigen
functions, Eigen values, Application of Schrodinger wave equation to (i) one dimensional
potential box of infinite height(InfinitePotential Well) and (ii) one dimensional harmonic
oscillator
The classical mechanics fails to explain the microscopic system of
particles due to uncertainty principle. According to uncertainty principle, the position and
momentum of a particle can’t be measured accurately at the same time. The measurement of one
quantity introduces an uncertainty into the other. According to de-broglie, a material particle is
associated with a wave. So, a mathematical reformation using a wave function associated with
matter waves is needed. So, quantum mechanics was developed in 1926 by schroedinger.
Basic postulates of quantum mechanics :
SCHROEDINGER WAVE EQUATION:
(1) TIME INDEPENDENT WAVE EQUATION:
According to de-broglie theory, a particle of mass m is always associated with a wave whose
h
wavelength is given by  = .Consider a system of stationary waves associated with a
mv
particle. Let x, y, z be the coordinates of the particle and  be the displacement for the de-broglie
at any time t.  is called wave function. Here  is finite, single valued and periodic function.
The classical differential equation of a wave motion is given by
 2 2  
2
 2  2 
= v 
 + + 2  = v 2  2 − − − − − − − − − − − −(1)
t 2
 x
2
y 2
z 
2 2 2
Where  2 = + + here  2 is the laplacian operator
x 2
y 2
z 2

v=wave velocity
The solution of eq (1) is given by
 =  0 sin t =  0 sin 2t − − − − − − − − − −(2)
Where  =frequency of stationary wave
Differentiating the above equation we get

=  0 2 cos 2t
t
 2
= − 0 (2 ) sin 2t
2

t 2

 2 4 2 v 2
= − 4 
2 2
 = −  − − − − − − − − − − − (3)
t 2 2
By substituting the above value in eq (1) we get

GMS-27
 4 2 v 2
v 2  2 = − 
2
4 2
 2 +  =0
2
4 2
 2 + 2
m 2 v 2 = 0 − − − − − − − − − − − − − − − − − ( 4)
h
If E and V be the total and potential energies of the particle respectively the K.E is given by
1 2
mv = E − V
2
m2v 2
= E − V = m 2 v 2 = 2m(E − V ) − − − − − − − − − −(5)
2m
From eq (4) and eq (5) we have
4 2
 2 + 2 2m(E − V ) = 0 − − − − − − − − − (6)
h
This is the schroedinger time dependent wave equation
Eq (6) can be written as
 2 + 2 (E − V ) = 0
2m

2

 2 + (E − V ) = 0
2m
2 2
  − V = − E
2m
 2 2 
− 2m  + V  = E
 
Hˆ  = E
 2 2 
Here Hˆ = −  +V 
 2m 
And H is known as Hamiltonian operator
For a free particle v=0
2mE
 2 + 2  = 0 − − − − − − − − − − − (7)

(2) SCHROEDINGER TIME DEPENDENT WAVE EQUATION:
In order to derive time dependent wave eq, schroedinger introduced a mathematical
function  which is variable quantity associated with the moving particle. This is a complex
function of space coordinates of the particle and time.
The differential equation representing a one dimensional wave motion is
 2
= v 2  2 − − − − − − − − − − − − − − − (1)
t 2

The solution of the above equation with respect to time t, we get

 (x, y, z, t ) =  0 (x, y, z )e −it − − − − − − − − − − − (2)

GMS-28
Differentiating the above equation w.r.t to time t we get

=  0 (− i )e −it
t
E − iE
=  0 (− i 2v )e −it = −2iv = −2i   = 
h 

E = i − − − − − − − − − − − − − − − − − −(3)
t
Substituting the above value in schroedinger time independent wave eq we get
2m   
 2 + 2 i − V  = 0
  t 
− 2m   
 2 = 2 i − V 
  t 
− 2

 2 + V = i − − − − − − − − − − − − − − − (4)
2m t
This eq is known as schroedinger time dependent wave equation.
Eq (4) can be written as

− 2 2  
[  + V ] = i − − − − − − − − − − − − − − − (5) Here Eˆ = i =energy operator
2m t t
or Hˆ  = Eˆ 
Eq (5) describes the motion of a non-relativistic material particle.
PHYSICAL SIGNIFICANCE OF WAVE FUNCTION :
The interpretation of  was given by schroedinger himself in terms of charge density. If
A is the amplitude of electromagnetic wave then the energy density is equal to A2 .Hence photon
A2
density is equal to or photon density is proportional to A2. If  is the amplitude of matter
h
waves at any point in space, then the particle density at that point is proportional to 2 therefore
 2 is a measure of particle density. When this is multiplied by the charge of the particle, the
charge density is obtained.
It is observed that in some cases,  is appreciably different from zero with in a wave
packet. To explain it, max born suggested a new idea about physical significance of .According
to Max born  * =  gives the probability of finding the particle in the state . 2 is a
2

measure of probability density. The probability of finding the particle in volume d = dxdydz is
given by  dxdydz . For the total probability of finding the particle somewhere in space is unity.
2

  dxdydz = 1
2

 Satisfying the above requirement is said to be normalized.

Wave function properties:
1) IT MUST BE FINITE EVERYWHERE:

GMS-29
 If  is infinite at a particular point, then it would mean an infinitely
large probability of finding the particle at that point.
This is not possible hence  it must have a finite or zero value at any point.
2) IT MUST BE SINGLE VALUED:
Let us consider that  has more than one value at any point. It means
that there is more than one value of probability of finding the particle at that point.
3) IT MUST BE CONTINUOUS:
d 2
For Schrödinger equation
dx 2
d
Must be finite everywhere. This is possible only when has no discontinuity at any boundary
dx
where potential changes. Hence too must be continuously
across a boundary.
Application of Schrodinger wave equation to particle in one
dimensional infinite box:
Let us consider the case of a particle of mass m moving along the
x-axis between two rigid walls A and B at x=0 and x=  . The
particle is free
to move between the walls. The potential energy of the particle
between the two walls is constant because no force is acting on
the particle. The constant potential energy is taken as zero for
simplicity. When the particle strikes any one of the walls, it is
reflected back immediately .Now the force acting on the particle
abruptly changes from zero to a finite value F within a distance of
zero at the wall. The potential function is defined in the following
way
v(x ) =  For x<0 and x>a
v(x ) = 0 For 0  x  a
Schrödinger wave equation for the particle is given by
d 2 8 2 m
+ 2 (E − V ) = 0
dx 2 h
As V=0 between the walls, hence the eqn. becomes
d 2 8 2 m
+ E = 0 − − − − − − − −(1)
dx 2 h2
8 2 m
Let 2
E = K 2 then the above eq. becomes

d 2
2
+ K 2 = 0 − − − − − − − − − − − −(2)
dx
The general solution of the above eqn. is given by
 (x ) = Asin kx + B cos kx
Where A and B are constants
By applying boundary conditions we can determine the value of constants A and B. The particle
can’t penetrate the walls, hence =0 at x=0 and  =0 at x=a these are the boundary conditions.

GMS-30
Hence
0=Asin0+Bcos0 i.e. B=0
 (x) = A sin kx
Again 0=A sin ka  (x ) = 0 when x=a
Here A  0 hence ka=0
sin ka=0 or ka=n  n=0,1,2
n
k= − − − − − − − (3)
a
Now the wave function becomes
nx
 (x ) = A sin − − − − − − − (4)
a
EIGEN VALUES: From eqn. (3) we have
n 2 2
k 2 = 2 − − − − − − − (5)
a
8 2 mE
And also k =
2
− − − − − − − − − − − −(6)
h2
From eq (5) and eq (6) we have
n 2 2 8 2 mEn
=
a2 h2
n2h2 2  
2 2
En = =n − − − − − − − − − − − (7 )
8ma 2 2ma 2
From esq. (7) it is clear that inside an infinitely deep potential wall, the particle can have only
discrete set of values of energy. Hence the energy of the
particle is quantized.
 2 2
If n=1 then E1 =
2ma 2
4 2  2
n=2 then E 2 = = 4 E1
2ma 2
9 2  2
n=3 then E3 = = 9 E1
2ma 2
16 2  2
n=4 then E 4 = = 16 E1
2ma 2
The energy level is as shown in the fig (2)
WAVE FUNCTION: by applying normalization condition we get fig (2)

GMS-31
 a 2

  ( x)
0
dx = 1

nx
a

A dx = 1
2
sin 2
0
a
2nx 
a
1
 2 1 − cos dx = 1
2
A
0
a 
2nx 
a
A  2
a
 x− sin =1
2  2n a  0

fig (3)
A2 a 2 2
= 1 Or A2 = or A=
2 a a
nx
 (x ) =
2
sin − − − − − − − − − − − − − −(8)
a a
The above Eqn. represents, the wave function of the particle enclosed in infinitely deep potential
well. The wave functions  1 , 2 and  3 corresponding to n=1,2and3 are
shown in fig (3)

PROBABILITY DENSITY: The probability of finding the particle

nx
between portions x and x+dx is given by P(x ) =  dx = sin
2 2
dx
a a

nx
Probability density P( x ) =
2
sin
a a
nx  3 5
It is maximum when = , , ................
a 2 2 2
a 3a 5a
Or x = , , ..............
2n 2n 2n
For n=1 the particle is most likely to be found at the middle of the box because  1
2
is
maximum at x=a/2 for n=2, x=a/4 and 3a/4 i.e. the particle is most likely too be found at x=a/4
and 3a/4 because  2 is maximum at that points. Similarly, for n=3 the particle is most likely to
2

be found at x=a/6,3a/6,5a/6.the variation of probability densities  1 ,  2 and  3 . For n=1, 2

2 2 2

and 3 are shown in the fig.

dx
According to classical mechanics, a particle moving with a velocity v spends a time in
v
traveling distance dx and hence the probability distribution is constant. According to

GMS-32
Quantum mechanics the probability of the particle being present is different for different
quantum numbers.
Quantum mechanics results vary drastically from classical results. The classical mechanics
predicts the same probability for the particle being any where in the box while quantum
mechanics predicts that the probability is different at different points.

GMS-33
 UNIT-IV:
NUCLEAR PHYSICS
SYLLABUS: Nuclear Structure: General Properties of Nuclei, Mass defect, Binding energy;
Nuclear forces: Characteristics of nuclear forces- Yukawa’s meson theory; Nuclear Models:
Liquid drop model, The Shell model, Magic numbers; Nuclear Radiation detectors: G.M.
Counter, Cloud chamber, Solid State detector; Elementary Particles: Elementary Particles and
their classification
INTRODUCTION: From the scattering of  particles, Rutherford concluded that the atom of
any element consists of central core called nucleus and electrons moving around it. The entire
mass of the atom and positive charge is concentrated inside the nucleus.
Mass of electron=9.1x10-31kg
Mass of Proton=1.673x10-27kg
Mass of Neutron=1.674x10-27 kg
The number of protons in the nucleus is called atomic number and the sum of protons and
neutrons is called as mass number. The stability of the nucleus depends upon the relative number
of protons and neutrons.
BASIC PROPERTIES OF NUCLEUS:
(a) NUCLEAR MASS:
The mass of the nucleus is the sum of the masses of the neutrons and protons. It is
expressed in terms of atomic mass unit
1 a.m.u=1.66x10-27kg=9.315MeV
EX: mass of 6C12 is 12 a.m.u
Mass of the nucleus =Zmp +Nmn where mp=mass of proton
Real nuclear mass< Zmp+Nmn mn=mass of neutron
The difference of the mss is called mass defect. The mass defect is converted into energy
according to E=mc2 formula.
(b) NUCLEAR CHARGE:
The charge on the nucleus is due to protons contained in it. The charge on each proton is
+1.6x10-19 coulomb. This is equal in magnitude to the charge of an electron. For example, a
hydrogen nucleus carries a single unit charge.,
(c) NUCLEAR RADIUS:
Nuclear diameter can be determined by the experiments like scattering of fast protons or
neutrons or scattering of high energy of electrons. Rutherford concluded that the distance of the
closest approach of the  particle to the nucleus of the scatter can be regarded as a measure of
the size of the nucleus. He found this distance of the order of 10-14m. This can be determined
from the empirical formula
r=roA1/3
Where ro=linear constant 1.4x10-15m
` A= mass of the nucleus.
EX :( 1) Carbon (A=12) : r=1.4x10-15x (12)1/3=3.21X10-15m
(2) Copper (A=63) : r=1.4x10-15(63)1/3=5.97x10-15m
(3) Uranium (A=238): r=8.68x10-15m
NUCLEAR DENSITY:
Density of Nucleus =mass of the Nucleus/volume of the Nucleus
4
= (mass number x mass of proton)/ r 3
3

GMS-34
 AX 1.673 X 10−27
= 3
4  
1
 1.5 X 10−15 A 3 
3  
1.673 X 10−2 A
= − 45
= 1.18 x1017 kg / m3
14.15 X 10 A
NUCLEAR QUANTUM STATES:
Every nucleus possesses a set of quantum states in a corresponding number of discrete
energy levels. Transition between different nuclear states is accompanied by the emission of 
rays.
NUCLEAR SPIN:
In atomic spectra, we found many spectral lines which have fine structure. That was
explained by electron spin. Many of these fine structure lines show still finer structure called
“hyper fine structure” which has been attribute to the nuclear spin.
Both the proton and the neutron have an intrinsic angular momentum generally it is called
as its spin.
1 h
The magnitude of the spin angular momentum is  where  = . The nucleons [protons and
2 2
neutrons] possess orbital angular momentum due to motion about the centre of the nucleus. The
resultant angular momentum I of the nucleon is obtained by adding spin and orbital angular
momentum of all nucleons in the nucleus.
Total angular momentum I =L+S
Where L=orbital angular momentum
S=spin angular momentum
MAGNETIC DIPOLE MOMENT OF NUCLEI (  ):
We know that the charged particle moving in a closed path produces a magnetic field.
The spinning electron is associated with a magnetic dipole moment of one “Bhor magneton”
e
i.e.,  e = where e is the charge me is the mass of the electron.
2me
e
Due to proton spin, it has Magnetic dipole moment  N = where mp is the proton mass
2m p
and μ N is called nuclear magneton.
1
Since mp=1836xme so nuclear magneton of a Bohr magneton.
1836
Neutron is a neutral particle. So it is very difficult to understand how it can have a
magnetic moment. It is found that neutron has a magnetic moment n = −1.9128N . To explain
 n , it was assumed that neutron contains equal amount of +ve and –ve charges. If these charges
are not uniformly distributed then a spin magnetic moment may arise. The magnetic moments of
nuclei are found to vary between -2 to +4 nuclear magneton.
ELECTRIC QUADRUPOLE MOMENT (Q): Experiments show that the shape of the nucleus
is not spherical but it is an ellipsoid of revolution. The derivation from the spherical symmetry is
measured by a quantity called its electric quadrupole moment.

GMS-35
 If the axis of symmetry is 2a and the diameter in the perpendicular direction is 2b, the
electric quadrupole moment is defined as
Q= ze(b 2 − a 2 )
2
5
Where z is atomic number and Ze is total charge of nucleus.
Therefore Q = 0 for spherical shaped nucleus, Q is negative for a > b and Q is positive for b > a
as shown in the above fig.
BINDING ENERGY OF NUCLEUS:
When protons and neutrons combine to form a nucleus, some of the mass (m) is found
to be disappeared. This is known as mass defect. This m mass is converted into an amount of
energy equal to (m)c 2 . This energy is called the binding energy of the nucleus. To separate a
stable nucleus into its constituent protons and neutrons, the minimum energy required is the
binding energy. If the binding energy is large the nucleus is stable.
If M is the mass of the nucleus having Z protons and N neutrons then
B.E= [(Zmp+Nmn)-M] c2
Where, mp and mn are the mass of proton and neutron respectively. If B.E<0, the nucleus is
unstable and it will disintegrate by itself.

The ratio of binding energy of the nucleus and number of nucleons in it is known as B.E
per nucleon. The B.E per nucleon is plotted as function of mass number A in the above fig. from
the graph it is clear that nuclei of intermediate mass[A=40 to 140] are most stable nuclei. The
binding energies of He 4 , C 12 , O16 are considerably greater than those of their neighbors.
When a heavier nucleus splits into lighter nuclei or lighter nuclei join to form heavier
nucleus energy is released. The first process is called nuclear fission and the second is called
nuclear fusion.
BINDING ENERGY OF DEUTRON:
The isotopes of hydrogen are 1H1 and 1H2. The heaviest isotope of hydrogen is called
deuteron. It consists of one proton and one neutron in its nucleus.
B.E of 1H2 =total mass of proton and neutron-actual mass of 1H2

GMS-36
 B.E of 1H2 = (2.016490-2014104)a.m.u
=0.002386x931 MeV
=2.23 MeV
This shows that when a proton and neutron are combined to form a deuteron, energy equal to
2.23 MeV is released.
NUCLEAR MODELS:
The force that binds the proton and the neutron so securely into a tiny molecule is the
strongest type of force known. This nucleus force is a short range force. To explain the nuclear
properties, theoretical physicist developed various nuclear models. They are (1) liquid drop
model and (2) shell model
LIQUID DROP MODEL:
This model was proposed by Neil’s Bhor in 1937. According to this model
(1) The nucleus is similar to a small electrically charged liquid drop i.e., nucleus take a
spherical shape for its stability.
(2) The nucleons move within this spherical enclosure like molecules in a liquid drop.
(3) The motion of nucleons within nucleus is a measure of nuclear temperature as the
molecular motion of molecules in liquid is the measure of its temperature.
(4) The nucleons always remains constant distant a part and share among them the total
energy of the nucleus.
(5) The nucleons inside the nucleus are attracted from all sides by neighboring nucleons
while those on the surface are attracted from one side only. In this way the binding
energy for the nucleons at the surface of the nucleus is smaller than the binding energy
for the nucleons inside the nucleus.
In this model the nucleus is regarded as arranged to a drop of liquid. Hence this model is
known as liquid drop model.
FOLLOWING ARE THE ANALOGIES BETWEEN LIQUID DROP AND A NUCLEUS:
(1) Both are spherical in nature.
(2) In both the cases, the density is independent of its volume.
(3) The molecules in liquid drop interact over short ranges and so is true for nucleons in nucleus.
(4) As the surface tension forces act on the surface of a drop similarly a potential barrier acts on
the surface of nucleus.
(5) When the temperature of the molecules in a liquid drop increased, evaporation of molecules
takes place. Similarly, when the nucleons in the nucleus are subjected to external energy, a
compound nucleus is formed which emits nucleons almost immediately.
MERITS:
(1) It has been successfully explains nuclear reactions and nuclear fission.
(2) The calculations of atomic mass and binding energy can be done with good accuracy.

DE-MERITS:
This model fails to explain other properties like magic numbers (2, 8, 20, 28, 50, and 82,126).
THE SHELLMODEL:
The nucleus consists of a series of protons and neutrons placed in certain discrete levels
or shells just like the electrons in the discrete shells of an atom. According to Pauli’s exclusion
principle two protons with opposite spins and two neutrons having opposite spins are
accommodated in a particular shell. In this way the first shell accommodates two protons and
two neutrons and is more tightly bound than other shells.

GMS-37
THE CONCEPT OF THE SHELL MODEL IS BASED ON THE FOLLOWING FACT:
It has been observed that the nuclei containing protons and neutrons numbers 2,
8,20,50,82,126 called magic numbers are exceptionally stable. This shows that there are definite
energy shells in the nuclei.
In 1949 Maria-Mayer and Jensen proposed that magic numbers can be obtained by
assuming that there is strong interaction between the spin angular momentum S and the orbital
angular momentum L of the nucleon. If we write j=l + s. we get two values. They are l+s and l-s.
The energy depends on total angular momentum quantum number j. for each value of j there will
be 2j+1 different states corresponding to different projections of j on the Z-axis. Thus there will
be 2j+1nucleons in a state of given j.

As shown in the fig, the energy levels are grouped into shells such that each shell
contains closely spaced energy levels and two consecutive shells are separated by a large gap.
The closed shells are obtained ,whenever the number of nucleons are 2,8,20,28,50 etc… Thus
magic numbers are obtained. The shell structure applies to both neutrons and protons separately.

MERITS:
This model explains the magic numbers, observed angular momenta, magnetic moments
and quadrupole moments of nuclei.
DE-MERITS:
This model fails to explain the large nuclear quadrupole moment and spherical shapes of
many nuclei.
Magic numbers: In nuclear physics, a magic number is a number of nucleons
(either protons or neutrons, separately) such that they are arranged into complete shells within
the atomic nucleus. The seven most widely recognized magic numbers are 2, 8, 20, 28, 50, 82,
and 126 .For protons, this corresponds to the elements helium, oxygen,
calcium, nickel, tin, lead and the hypothetical element 126 or eka-plutonium, although 126 is so
far only known to be a magic number for neutrons. Atomic nuclei consisting of such a magic
number of nucleons have a higher average binding energy per nucleon than one would expect
based upon predictions such as the semi-empirical mass formula and are hence more stable
against nuclear decay.
Parity: Parity is a fundamental characture of nucleus. Parity can be even or odd depending on
nucleon number of the atomic nucleus.
In physics, property important in the quantum-mechanical description of a physical system. In
most cases it relates to the symmetry of the wave function representing a system of fundamental
GMS-38
particles. A parity transformation replaces such a system with a type of mirror image. Stated
mathematically, the spatial coordinates describing the system are inverted through the point at
the origin; that is, the coordinates x, y, and z are replaced with −x, −y, and −z. In general, if a
system is identical to the original system after a parity transformation, the system is said to have
even parity. If the final formulation is the negative of the original, its parity is odd. For either
parity the physical observables, which depend on the square of the wave function, are
unchanged. A complex system has an overall parity that is the product of the parities of its
components.

G.M COUNTER:
DESCRIPITION:
As shown in the fig G.M
counter consists of a fine wire of
tungsten along the axis of cylinder
copper tube. The tube contains a gas
at a pressure of about 10cm of Hg.
This gas is a mixture of 90% argon
and 10% ethyl alcohol. The
ionization particles enter into the
chamber through mica window. A
potential difference of about 800V to
2000V is applied between the copper
tube [cathode] and the tungsten wire
[anode] by means of a battery. A high resistance R is also connected in series with the battery.
WORKING:
When the charged particle is allowed to pass through the window, it ionizes the gas molecules
inside the tube. Hence +vely charged ions and electrons in pairs are produced. The anode attracts
the electrons while the cathode attracts the +ve ions. Hence the ionization current is produced
and it depends upon the applied voltage. At sufficiently high voltages, the electrons gain high
K.E and cause further ionization of argon atoms. Hence large no: of secondary electrons are
produced.
The incoming particle serves the purpose of triggering the release of an avalanche of
secondary electrons. The electrons quickly reach the anode and produce ionization current. The
+ve ion move more slowly away from anode and they form a sheath around the anode for a short
while. They reduce the potential difference between the electrodes to very low value. The current
therefore stops. In this way brief pulse of current flows through the resistance R. this current
creates a potential difference across R. the pulse is amplified and fed to counter circuit. As each
incoming particle produces a pulse, hence the no: of particles can be counted.
VOLTAGE CHARACTERISTIC CURRENT:
If we draw a graph by taking voltage on X-axis and count
per minute on Y-axis then the graph is as shown in the fig.
From the graph it is clear that the current pulses are too
small to be detect until the applied voltage reaches the value
indicates as the threshold voltage. As the P.D increases the
ionization also increases and the pulse rate increase rapidly
upto a flat portion called the plateau. In this region count rate

GMS-39
is nearly independent of the P.D .Beyond the plateau, if the voltage is increased a continuous
discharge will takes place. This is un-desirable.
QUENCHING: When +ve ions of high K.E reach the walls of the tube, then electron emission
takes place from metal cathode. These electrons travel towards the anode and produce un-wanted
pulse in a continuous process. The method used to prevent a continuous series of pulses is called
Quenching. The self quenching is obtained by adding alcohol vapour inside the tube. Alcohol has
low ionization potential. The argon ions on their journey to the cathode are neutralized by
acquiring an electron from the alcohol molecules. Now only alcohol ions reach the cathode and
become neutral. The K.E of alcohol molecules is used for dissociation of alcohol atoms. Thus it
is a self quenching.
In G.M counter the slowly moving +ve ions take about 100  s to reach the cathode. This
time is known as dead time. If a second particle enters the tube during this time, it will not be
recorded as the P.D across the electrodes is very low. After dead time, the tube takes nearly 100
 s before it regains its original condition. This time interval is known as recovery time. The
sum of these two is known as paralysis time. Hence G.M counter can count nearly 500 particles
per second.
ADVANTAGES:
(1) This G.M counter is very useful to detect and counting  particles.
(2) It is very useful to study the cosmic rays.
DIS ADVANTAGES:
It can’t give information as charge, momentum, energy, range of the particles.
WILSON CLOUD CHAMBER:
In 1931 Wilson designed an
instrument known as cloud chamber it is
used to detect and record the paths of
charged particle.
PRINCIPLE:
If a saturated water vapour
undergoes a sudden expansion, then due to
cooling the vapour gets super saturated. At
this instant of expansion, if an ionizing
particle enters the chamber, the ions it
produces becomes condensation centers of
the molecules of super saturated vapour. By
illuminating the chamber, we can record
the ion tracks by using camera.
CONSTRUCTION:
The experimental arrangement is as shown in the fig. it consists of an air-tight cylinder C
provided with a movable piston P and upper end covered with a glass plate G. the chamber
contains a mixture of alcohol vapour and air. A small amount of water and alcohol is kept in a
trough at the lower end of the chamber. The chamber is illuminated by mercury vapour lamp.
The charged particle like or rays is allowed to enter the chamber by a side window. A camera
is adjusted on the upper side of the chamber.
WORKING: The air inside the chamber is cooled and becomes super saturated by suddenly
increasing the volume of the chamber by using piston P. as a result alcohol vapour condenses
into drops forms fog in the chamber. When or rays are allowed to enter in the chamber, they

GMS-40
ionize the gas. Now –ve and +ve ions are formed all along the path of these rays. If at the same
time expansion takes place, fog drops will be formed on newly created ions. A clear track in the
form of drop is thus formed. The drops are clearly visible when the chamber is illuminated by
light. The track can be photographed with the help of camera. Immediately after this, the track is
removed by applying an electric field across the air gap. Now the chamber gets ready for the next
photograph.
ADVANTAGES:
(1) It is used for the study of radioactive radiations.
(2) By counting drops in cloud track, the specific ionization can be determined.
(3) It is used for recording the tracks of ionizing particles.
(4) By seeing the direction of track in the magnetic field, the sign of the ionizing particle can
be determined.
DIS-ADVANTAGES:
(1) If the range of the particle exceeds the dimensions of the chamber then the whole track is
not photographed.
(2) This cannot directly record the track of electrically neutral particles like neutrons.
(3) It is not continuously sensitive and hence there is a possibility of missing certain nuclear
reactions.

SOLID STATE DETECTOR(semiconductor radiation detector): In a semiconductor

radiation detector, incident radiation interacts with the detector material, a
semiconductor such as Si or Ge, to create hole electron pairs. These pairs are
collected by charged electrodes with the electro
ns migrating to the positive electrode and the holes to the negative electrode, thereby
creating an electrical pulse. Such pulses contain information on the type, energy, time of
arrival, and number of particles arriving per unit time.

FIGURE : Solid-state n-p junction detector

The important features of semiconductor detectors are their superior energy resolution due
to a lower ionization potential and compact size.

GMS-41
 Elementary Particles: A particle which does not have a sub structure or those microscopic
elementary constituents out of which all matter in this universe is considered to be made of. All
elementary particles are either bosons or fermions. These classes are distinguished by
their quantum statistics: fermions obey Fermi–Dirac statistics and bosons obey Bose–Einstein
statistics. Their spin is differentiated via the spin–statistics theorem. it is half-integer for
fermions, and integer for bosons.
Classification of elementary particles:

GMS-42
GMS-43
GMS-44
 UNIT-V
NANO MATERIALS
Nanomaterials – Introduction, Electron confinement, Size effect, Surface to volume ratio,
Classification of nano materials– (0D, 1D, 2D); Quantum dots, Nano wires, Fullerene, CNT,
Graphene(Mention of structures and properties),Distinct properties of nano materials (Mention-
mechanical,optical, electrical, and magnetic properties); Mention of applications of nano
materials.

Introduction: The concept of nanotechnology was first given by renowned physicist Richard
Feynman in 1959 and earned Nobel Prize. The term was also popularized by the invention of
scanning tunneling microscope and fullerene.
Nanomaterials are any type of material of nanosized thickness, i.e. less than 100
nm in thickness. There are various types, many of which exhibit different properties than bulk
materials. One common factor of nanomaterials is that this thickness range is also known as the
quantum regime, where quantum effects play a major role in defining the properties. Because of
this, nanomaterials often fall into different dimensional categories, be it 2D, 1D or 0D.
Electron confinement : Electron confinement or quantum confinement is another process that
occurs in nanoparticles. We know that when atoms are isolated, then their energy levels are
discrete but when they are in packed form and in large numbers (in solid form), the energy levels
split and form bands (band means group of levels). Nanoparticles represents intermediate stage.
Size effect: By size effect we mean a dependence of a material parameter such as Young’s
modulus on a specimen size which is used for the parameter determination.
The size of nanoparticles is vital to their characteristics and, therefore, their
function. Determining the size of nanoparticles is essential to understanding the characteristics
associated with different particle sizes, how they interact with other compounds, and how they
can be leveraged in different applications. In fact, it is reasonable to consider, based on the
microstructural results from XRD measurements, that decreasing particle sizes result in an
increase of the surface-to-volume ratio, which results in lattice contraction and, subsequently, the
inducing of micro strain in the crystalline lattice.
Surface to volume ratio: It means that the surface area to volume ratio increases as the radius
of the sphere decreases and vice versa. It also means that when a given volume of material is
made up of smaller particles, the surface area of the material increases.
A nanometre is one billionth of a metre (0.000 000 001 m). So, it may not
come as a surprise that nanoparticles of material show different properties compared to larger
particles of the same material. The surface area to volume ratio for a material or substance made
of nanoparticles has a significant effect on the properties of the material. Firstly, materials made
up of nanoparticles have a relative larger surface area when compared to the same volume of
material made up of bigger particles.
For example, let us consider a sphere of radius r The surface area of the sphere will
be 4πr The volume of the sphere = 4/3πr 3 Therefore the surface area to the volume ratio will be
2

4πr 2 /(4/3πr 3 ) = 3/r It means that the surface area to volume ratio increases as the radius of the
sphere decreases and vice versa. It also means that when a given volume of material is made up
of smaller particles, the surface area of the material increases. Therefore, as particle size
decreases, a greater proportion of the particles are found at the surface of the material. For
example, a particle of size 3 nm has 50% of its particles on the surface; at 10 nm, 20% of its

GMS-45
particles are on the surface; and at 30 nm, 5% of its particles are on the surface. Therefore,
materials made of nanoparticles have a much greater surface area per unit volume ratio compared
with the materials made up of bigger particles. This leads to nanoparticles being more chemically
reactive. As chemical reactions occur between particles that are on the surface, a given mass of
nanomaterial will be much more reactive than the same mass of material made up of large
particles.
Classification of nano materials– (0D, 1D, 2D): The classification of nanomaterials is based on
the number of dimensions as shown in the Fig. According to Siegel, nanostructured materials
are classified as: zerodimensional (0D), one-dimensional (1D), two-dimensional (2D) and
threedimensional (3D) nanomaterials.
(i) Zero-dimensional nanomaterials: Here, all dimensions (x, y, z) are at nanoscale, i.e.,
no dimensions
are greater
than 100 nm.
It includes
nanospheres
and
nanoclusters.
(ii) (ii) One-
dimensional
nanomaterials:
Here, two dimensions (x, y) are at nanoscale and the other is outside the nanoscale.
This leads to needle shaped nanomaterials. It includes nanofibres, nanotubes,
nanorods, and nanowires.
(iii) Two-dimensional nanomaterials: Here, one dimension (x) is at nanoscale and the
other two are outside the nanoscale. The 2D nanomaterials exhibit platelike shapes. It
includes nanofilms, nanolayers and nanocoatings with nanometre thickness.
(iv) (iv) Three-dimensional nanomaterials: These are the nanomaterials that are not
confined to the nanoscale in any dimension. These materials have three arbitrary
dimensions above 100 nm. The bulk (3D) nanomaterials are composed of a multiple
arrangement of nanosize crystals in different orientations. It includes dispersions of
nanoparticles, bundles of nanowires and nanotubes as well as multinanolayers
(polycrystals) in which the 0D, 1D and 2D structural elements are in close contact
with each other and form interfaces.
QUANTUM DOTS: Quantum dots (QDs) were first discovered by A. Ekimov in glass matrix
and by L. Brus in colloidal solutions (Fig. 2). These are the semiconductor nanoparticles between
10 and 100 atoms in diameter. The properties of QDs can vary depending on its shape and size.
These are not all uniform. In spite of having a variety of applications, QDs are a source of toxic
compounds containing in their core. The QDs toxicity may be due to the leaching of toxic heavy
metals from the colloid form. The toxicity may also be originated from intrinsic properties of the
size and surface chemistry of quantum dots. Such materials might have potential risks to human
health but still the use of these materials is growing quickly.

GMS-46
Fig. 2: Synthesis of Quantum dots (QDs)

Applications of Quantum dots:

1. These are used in transistors, solar cells, diode lasers, LEDs, etc.

2. These may increase the efficiency of silicon photovoltaic cells.

3. These are also significant for optical applications like amplifiers, biological sensors, etc.

4. These are used as photocatalysts.

5. They have potential applications in spectroscopy and fluorescent biomedical imaging.

NANOWIRES:
These are defined as the structures which have the diameters of the order of a nanometre and an
unconstrained length. i.e., nanowires are much longer than their diameters. These are also called
quantum wires because at this scale they have different quantum mechanical effects. There are
different types of nanowires. For example: carbon nanowires, molecular nanowires, metallic
nanowires, etc.
Applications:
1. They are useful in digital computing.

GMS-47
 2. These are used for the preparation of active electronic components like p-n junction, logic
gates, etc.

3. They have potential applications in high-density data storage.

4. Silver chloride nanowires are used as photocatalysts to decompose organic molecules in

polluted water.

Fullerene: The first fullerene was discovered by Harold Kroto, Richard Smalley and Robert
Curl in 1985 by using a laser to vaporise graphite rods in
an atmosphere of helium gas. The fullerenes (allotropes of
carbon) are graphene sheets rolled into tubes or spheres. It
is a cage like molecule composed of 60 carbon atoms
(C60) joined together by single and double bonds to form
a hollow sphere with 20 hexagonal and 12 pentagonal
faces (a design that resembles a football). It was named as
buckminsterfullerene or buckyball after the name of
American architect Buckminster Fuller, the inventor of the
geodesic dome. The structure of fullerene (C60) is shown
in Fig. 3.
Fig. 4 Fullerene (C60)
Applications:
The recent research has suggested that fullerence has many
uses, including medical applications, superconductors, fiber-optics, etc. Some of the important
applications are listed as follows:
1. (C60) and their derivatives have potential antiviral activity, and may be used for the
treatment of HIV-infection.

2. They have potential medicinal applications as they can bind specific antibiotics and target
certain types of cancer cells such as melanoma.

3. They are used as biological antioxidants.

4. They are also used as potential photosensitizers in photodynamic therapy and catalysts
for hydrogenation.

5. Fullerenes incorporated with sulphides of tungsten and molybdenum exhibit excellent

solid-lubricant properties.

NANOTUBES(CNT) :
The carbon nanotubes (elongated form of fullerenes) were identified in 1991 by Iijima Sumio of
Japan. A carbon nanotube is a tube-shaped material, made up of carbon, having a diameter

GMS-48
ranging from < 1 nm to 50 nm. Simply we can say, carbon nanotubes (CNTs) are cylinders of
one or more layers of graphene (lattice). Carbon nanotubes show a unique combination of
stiffness, strength, and tenacity compared to other fibre materials. Thermal and electrical
conductivity are also very high as comparable to other conductive materials. Carbon nanotubes
may be categorized as follows:
Single-wall nanotubes (SWNT): These may be zigzag, armchair and chiral depending on the
manner in which the grapheme sheets are rolled.

Multi-wall nanotubes (MWNT): It consists of several single

walled nanotubes with different diameters. A multi-wall
nanotube is shown in Fig. 5
Applications:Carbon nanotube technology can be used for a
wide range of new and existing applications, which are as
follows:
1. Nanotubes can potentially replace indium tin oxide in
solar cells to generate photocurrent.

2. SWNTs are used in transistors and solar panels.

3. MWNTs are used in lithium ion batteries to enhance cycle life.

4. Parallel CNTs have been used to create loudspeakers.

5. CNTs can serve as a multifunctional coating material.

6. CNTs can be used to produce nanowires.

7. CNTs are also used for applications in energy storage, automotive parts, boat hulls, water
filters, thin-film electronics coatings, ultra-capacitors, biosensors for harmful gases, extra
strong fibers, etc

GRAPHENE :
Graphene was first isolated by A.K. Geim and K.S. Novoselov at the University of Manchester
in 2004. They got Nobel Prize in 2010 for their pioneering work. Graphene is a crystalline
allotrope of carbon with two-dimensional, atomic scale,
hexagonal pattern. Here each carbon atom forms four bonds, three s bonds (sp2 hybridized) with
its three neighbours and one p bond oriented out of plane. It is the basic structural element of
other allotropes like graphite, fullerene, nanotubes, nanocones, etc. hence called mother of all
carbon nanomaterials (Fig. 3).

GMS-49
Properties:
1. It is nearly transparent.

2. It is 200 times stronger than steel by weight due to its

tightly packed carbon atoms.

3. It conducts heat and electricity with great efficiency

due to presence of p electrons.

4. Nowadays, it is commonly used in semiconductors,

batteries, electronics, composite industries, and many
more.

Fig. 3 Graphene and other carbon nanomaterials

PROPERTIES OF NANOMATERIALS:

Nanomaterials have the structural features in between of those of atoms and the bulk materials.
While most micro structured materials have similar properties to the corresponding bulk
materials, the properties of materials with nanometer dimensions are significantly different from
those of atoms and bulks materials. This is mainly due to the nanometer size of the materials
which render them: (i) large fraction of surface atoms; (ii) high surface energy; (iii) spatial
confinement; (iv) reduced imperfections, which do not exist in the corresponding bulk materials.
Optical properties:
Applications based on optical
properties of nanomaterials include
optical detector, laser,
sensor,imaging, phosphor, display,
solar cell, photocatalysis,
photoelectrochemistry and
biomedicine.

fig : 12
The optical properties of nanomaterials depend on parameters such as feature size, shape, surface
characteristics, and other variables including doping and interaction with the surrounding
environment or other nanostructures. Fig. (12) Exemplifies the difference in the optical
properties of metal and semiconductor nanoparticles. With the CdSe semiconductor
nanoparticles, a simple change in size alters the optical properties of the nanoparticles. When
metal nanoparticles are enlarged, their optical properties change only slightly as observed for the
different samples of gold nanospheres.
Electrical Properties:
Electrical Properties of Nanoparticles” discuss about fundamentals of electrical conductivity in

GMS-50
nanotubes and nanorods, carbon
nanotubes, photoconductivity of nanorods,
electrical conductivity of nanocomposites.
One interesting method which can be used
to demonstrate the steps in conductance
is the mechanical thinning of a nanowire
and measurement of the electrical
Fig :13

current at a constant applied voltage. The important point here is that, with decreasing diameter
of the wire, the number of electron wave modes contributing to the electrical conductivity is
becoming increasingly smaller by well-defined quantized steps.
In electrically conducting carbon nanotubes, only one electron wave mode is
observed which transport the electrical current. As the lengths and orientations of the carbon
nanotubes are different, they touch the surface of the mercury at different times, which provides
two sets of information: (i) the influence of carbon nanotube length on the resistance; and (ii) the
resistances of the different nanotubes.
Mechanical Properties:
“Mechanical Properties of Nanoparticles” deals with bulk metallic and ceramic materials,
influence of porosity, influence of grain size, superplasticity, filled polymer composites,
particlefilled polymers, polymer-based nanocomposites filled with platelets, carbon nanotube-
based composites.
The discussion of mechanical properties of nanomaterials is, in to some extent, only
of quite basic interest, the reason being that it is problematic to produce macroscopic bodies with
a high density and a grain size in the range of less than 100 nm. However, two materials, neither
of which is produced by pressing and sintering, have attracted much greater interest as they will
undoubtedly achieve industrial importance.
These materials are polymers which contain nanoparticles or nanotubes to improve their
mechanical behaviors, and severely plastic-deformed metals, which exhibit astonishing
properties. However, because of their larger grain size, the latter are generally not accepted as
nanomaterials. Experimental studies on the mechanical properties of bulk nanomaterials are
generally impaired by major experimental problems in producing specimens with exactly defined
grain sizes and porosities.
Magnetic properties:
Bulk gold and Pt are non-magnetic, but at the nano size they are magnetic. Surface atoms are not
only different to bulk atoms, but they can also be modified by interaction with other chemical
species, that is, by capping the nanoparticles. This phenomenon opens the possibility to modify
the physical properties of the nanoparticles by capping them with appropriate molecules.
Actually, it should be possible that non-ferromagnetic bulk materials exhibit ferromagnetic-like
behavior when prepared in nano range. One can obtain magnetic nanoparticles of Pd, Pt and the
surprising case of Au (that is diamagnetic in bulk) from non-magnetic bulk materials. In the case
of Pt and Pd, the ferromagnetism arises from the structural changes associated with size effects.
Fig. (14): Magnetic properties of nanostrucutred materials
However, gold nanoparticles become ferromagnetic when they are capped with appropriate
molecules: the charge localized at the particle surface gives rise to ferromagnetic-like behavior.

GMS-51
Surface and the core of Au nanoparticles with
2 nm in diameter show ferromagnetic and
paramagnetic character, respectively. The
large spin-orbit coupling of these noble metals
can
yield to a large anisotropy and therefore
exhibit high ordering temperatures. More
surprisingly,
permanent magnetism was observed up to
room temperature for thiol-capped Au
nanoparticles.
For nanoparticles with sizes below 2 nm the
localized carriers are in the 5d band. Bulk Au
Fig. (14)

has an extremely low density of states and becomes diamagnetic, as is also the case for bare Au
nanoparticles. This observation suggested that modification of the d band structure by chemical
bonding can induce ferromagnetic like character in metallic clusters.
APPLICATION OF NANOMATERIALS:
Nanomaterials having wide range of applications in the field of electronics, fuel cells, batteries,
agriculture, food industry, and medicines, etc... It is evident that nanomaterials split their
conventional counterparts because of their superior chemical, physical, and mechanical
properties and of their exceptional formability.

1) Fuel cells:
A fuel cell is an electrochemical energy conversion
device that converts the chemical energy
from fuel (on the anode side) and oxidant (on the
cathode side) directly into electricity. The heart
of fuel cell is the electrodes. The performance of a
fuel cell electrode can be optimized in two
ways; by improving the physical structure and by
using more active electro catalyst. A good
structure of electrode must provide ample surface
area, provide maximum contact of catalyst,
reactant gas and electrolyte, facilitate gas transport
and provide good electronic conductance. In
this fashion the structure should be able to minimize
losses.

2) Carbon nanotubes - Microbial fuel cell:

Microbial fuel cell is a device in which bacteria
consume water-soluble waste such as sugar,
starch and alcohols and produces electricity plus clean water. This technology will make it

GMS-52
possible to generate electricity while treating domestic or industrial wastewater. Microbial fuel
cell can turn different carbohydrates and complex substrates present in wastewaters into a source
of electricity. The efficient electron transfer between the microorganism and the anode of the
microbial fuel cell plays a major role in the performance of the fuel cell. The organic molecules
present in the wastewater posses a certain amount of chemical energy, which is released when
converting them to simpler molecules like CO2. The microbial fuel cell is thus a device that
converts the chemical energy present in water-soluble waste into electrical energy by the
catalytic reaction of microorganisms.
3) Carbon nanotubes : (CNTs) have chemical stability, good mechanical properties and
high surface area, making them ideal for the design of sensors and provide very high
surface area due to its Structural network. Since carbon nanotubes are also suitable
supports for cell growth, electrodes of microbial fuel cells can be built using of CNT.
4) Catalysis:
Higher surface area available with the nanomaterial counterparts, nano-catalysts tend to have
exceptional surface activity. For example, reaction rate at nano-aluminum can go so high, that it
is utilized as a solid-fuel in rocket propulsion, whereas the bulk aluminum is widely used in
utensils. Nano-aluminum becomes highly reactive and supplies the required thrust to send off
pay loads in space. Similarly, catalysts assisting or retarding the reaction rates are dependent on
the surface activity, and can very well be utilized in manipulating the rate-controlling step.
5) Phosphors for High-Definition TV
The resolution of a television, or a monitor, depends greatly on the size of the pixel. These pixels
are essentially made of materials called "phosphors," which glow when struck by a stream of
electrons inside the cathode ray tube (CRT). The resolution improves with a reduction in the size
of the pixel, or the phosphors. Nanocrystalline zinc selenide, zinc sulfide, cadmium sulfide, and
lead telluride synthesized by the sol-gel techniques are candidates for improving the resolution of
monitors. The use of nanophosphors is envisioned to reduce the cost of these displays so as to
render high-definition televisions (HDTVs) and personal computers affordable to be purchase.
6) Next-Generation Computer Chips
The microelectronics industry has been emphasizing miniaturization, whereby the circuits, such
as transistors, resistors, and capacitors, are reduced in size. By achieving a significant reduction
in their size, the microprocessors, which contain these components, can run much faster, thereby
enabling computations at far greater speeds.
Nanomaterials help the industry break these barriers down by providing the manufacturers
with nanocrystalline starting materials, ultra-high purity materials, materials with better thermal
conductivity, and longer-lasting, durable interconnections.
For example: Nanowires for junctionless transistors:
Transistors are made so tiny to reduce the size of sub assemblies of electronic systems and make
smaller and smaller devices, but it is difficult to create high-quality junctions. In particular, it is
very difficult to change the doping concentration of a material over distances shorter than about
10 nm. Researchers have succeeded in making the junctionless transistor having nearly ideal
electrical properties. It could potentially operate faster and use less power than any conventional
transistor on the market today. The device consists of a silicon nanowire in which current flow is
perfectly controlled by a silicon gate that is separated from the nanowire by a thin insulating
layer. The entire silicon nanowire is heavily n-doped, making it an excellent conductor.
However, the gate is p-doped and its presence has the effect of depleting the number of electrons
in the region of the nanowire under the gate. The device also has near-ideal electrical properties

GMS-53
and behaves like the most perfect of transistors without suffering from current leakage like
conventional devices and operates faster and using less energy.
Fig. (16): Silicon nanowires in junctionless transistors
7) Elimination of Pollutants
Nanomaterials possess extremely large grain boundaries relative to their grain size. Hence, they
are very active in terms of their chemical, physical, and mechanical properties. Due to their
enhanced chemical activity, nanomaterials can be used as catalysts to react with such noxious
and toxic gases as carbon monoxide and nitrogen oxide in automobile catalytic converters and
power generation equipment to prevent environmental pollution arising from burning gasoline
and coal.
8) Sensors
Sensors rely on the highly active surface to initiate a response with minute change in the
concentration of the species to be detected. Engineered monolayers (few Angstroms thick) on the
sensor surface are exposed to the environment and the peculiar functionality (such as change in
potential as the CO/anthrax level is detected) is utilized in sensing.
DISADVANTAGES OF NANOMATERIALS:
_ Instability of the particles : Retaining the active metal nanoparticles is highly
challenging, as the kinetics associated with nanomaterials is rapid. In order to retain
nanosize of particles, they are encapsulated in some other matrix. Nanomaterials are
thermodynamically metastable and lie in the region of high-energy local-minima. Hence
they are prone to attack and undergo transformation. These include poor corrosion
resistance, high solubility, and phase change of nanomaterials. This leads to deterioration
in properties and retaining the structure becomes challenging.
Fine metal particles act as strong explosives owing to their high surface area coming in
direct contact with oxygen. Their exothermic combustion can easily cause explosion.
_ Impurity : Because nanoparticles are highly reactive, they inherently interact with
impurities as well. In addition, encapsulation of nanoparticles becomes necessary when
they are synthesized in a solution (chemical route). The stabilization of nanoparticles
occurs because of a non-reactive species engulfing the reactive nano-entities. Thereby,
these secondary impurities become a part of the synthesized nanoparticles, and synthesis
of pure nanoparticles becomes highly difficult. Formation of oxides, nitrides, etc can also
get aggravated from the impure environment/ surrounding while synthesizing
nanoparticles. Hence retaining high purity in nanoparticles can become a challenge hard
to overcome.
_ Biologically harmful: Nanomaterials are usually considered harmful as they become
transparent to the cell-dermis. Toxicity of nanomaterials also appears predominant owing
to their high surface area and enhanced surface activity. Nanomaterials have shown to
cause irritation, and have indicated to be carcinogenic. If inhaled, their low mass entraps
them inside lungs, and in no way they can be expelled out of body. Their interaction with
liver/blood could also prove to be harmful (though this aspect is still being debated on).
Difficulty in synthesis, isolation and application - It is extremely hard to retain the size of
nanoparticles once they are synthesized in a solution. Hence, the nanomaterials have to
be encapsulated in a bigger and stable molecule/material.

GMS-54
 SUPER CONDUCTIVITY
SYLLABUS: Introduction to Superconductivity, Experimental results-critical temperature,
critical magnetic field, Meissner effect , Isotope effect,Type I and Type II superconductors, BCS
theory (elementary ideas only),Applications of superconductors
INTRODUCTION:
It was discovered by Kamerling onnes in 1911, when he was measuring the resistivity of
mercury at low temperatures. The electrical resistance of pure
mercury

drops suddenly to zero at 4.15K

TRANSISTION TEMPERATURE:
The temperature at which the resistance dis-appears is
called the transition temperature or critical temperature.
SUPER CONDUCTIVITY:
When the electrical resistance of a substance drops suddenly to zero, when the specimen
is cooled below a certain temperature is known as super conductivity.
BASIC EXPERIMENTAL FACTS:
The following are the experimental facts of superconductivity materials
(1) At room temperature, they have high resistivity.
(2) The critical temperature is different for different isotopes of an element.
(3) Tc decreases with increasing atomic weight of isotopes
(4) By adding impurities the superconductivity of a superconducting element is not lost but
its transition temperature is lowered.
(5) From X-ray diffraction studies it is clear that there is no change in the crystal structure.
Hence super conductivity may be due to electrons.
(6) Due to transition the thermal expansion and elastic property do not change.
(7) All thermo electric effects dis-appear in superconductors.
(8) The presence of a magnetic field causes a critical temperature Tc of the superconductor to
decrease.
(9) When a strong magnetic field above a critical field Bc is applied to a superconductor
below its transition temperature, the superconducting property is destroyed.
(10)Elements like copper and silver that are good conductors’ do not become
superconductors when cooled.
(11) Superconductor is perfectly diamagnetic. No magnetic field can exist inside a
superconductor.
(12) It can conduct electric current even in the absence of an applied voltage and the current
can persist for years without any detectable decay.

EXPLANATION OF SUPERCONDUCTIVITYAND ZERO RESISTANCE:

The electrical resistance of an ordinary metal is due to the collision between conduction
electrons and ions of the crystal. In a superconductor, the electrons are scattered in pairs due to

GMS-55
which an exchange force between electrons exists. This force is just similar to forces between the
nucleons in a nucleus. When the electron has opposite spins and momenta, there is very strong
attractive force between them. In superconducting state, the force of attraction is greater than the
electrostatic forces of repulsion. Thus all conduction electrons become a bound system. Now no
transfer of energy takes place from this system to lattice ions. When an electric field is applied to
a substance in superconducting state, the pairs of electrons gain additional K.E. thus they give
rise to a current. Since these electrons do not transfer energy to the lattice they are not transfer
energy to the lattice they are not slowed down. It means that the substance does not posses any
electrical resistivity. It means that the resistance of superconductor is zero.
EFFECT OF EXTERNAL FIELD:
In 1913, Kammerlingh onnes observed that, the superconducting material restores its
normal resistance when a strong magnetic field is applied.
The minimum value of applied magnetic field when the superconductor loses its
superconductivity is known as critical magnetic field Hc (o). If the applied magnetic field
exceeds the critical value Hc (o), the superconducting state is destroyed. This is shown in the
following figure.
From the fig it is clear that the normal state of the material is restored if the magnetic
field is greater than the critical value or the temperature is raised above critical temperature Tc.

MEISSNER EFFECT:

In 1933 Meissner observed that if a superconductor is cooled in a magnetic field, below

critical temperature corresponding to that field, than the lines of induction are expelled from the
material this effect is known as Meissner effect.

GMS-56
 As shown in the fig magnetic lines of force pass through the superconductor when it is in
the normal state. But when the specimen is cooled below its transition temperature the magnetic
lines of force are expelled out of the specimen.
IMPORTANT POINTS:
(1) Meissner effect is reversible.
(2) A superconductor is a perfect dia-magnetic.
(3) The difference between a perfect conductor and a superconductor is that the former is
only an ideal conductor while the later is simultaneously an ideal conductor and an ideal
dia-magnet.

EXPERIMENTAL DEMONSTRATION OF MEISSNER EFFECT:

As shown in the fig two coils are wounded on a superconductor. The superconductor is
above its critical temperature. In primary circuit, there is a battery and a plug key. The secondary
coil is connected to a galvanometer. When the key K is pressed, a current flow through the
primary coil as a result the galvanometer shows a momentary deflection. After that the primary
current becomes steady. Hence no deflection is observed in the B.G.
Now the temperature of superconductor is decreased gradually. As soon as the
temperature crosses below the critical temperature, the galvanometer shows a deflection. This
indicates that the flux linked with the secondary coil has changed. The change in magnetic flux is
due to expulsion of magnetic flux from superconducting material. This shows the experimental
demonstration of Meissner effect.
PERSISTANT CURRENT:
The resistance of the superconductor is zero at a temperature below its critical
temperature. That is in a superconductor currents can flow with no appreciable loss of energy.
This super current persists forever without any need for an external drilling emf.
It continues for a period of two and a half years observed by S.C. Collins. The decay time for
these persistent current is certainly more than 105 years.
IMPORTANT POINTS:
(1) Superconductivity is destroyed by application of a sufficiently large magnetic field.
(2) If the current exceeds a critical current the superconducting state will be destroyed.
GMS-57
ISOTOPE EFFECT:
It was discovered that the critical temperature of the isotope of a superconducting
element decrease with increasing atomic mass of the isotope. The Tc for the isotope 199Hg is
4.161K and for the isotope 204Hg is 4.126K. The isotope effect in its generalized form can be
stated as TcM1/2=constant
Here M is the mass of the isotope. This isotopic effect suggests that the current carrying
electrons in a superconductor do not move independently of ion lattice, instead of some low
interacting with the lattice. Thus the isotopic effect revealed that electron-photon interactions are
deeply involved in the phenomenon of superconductivity.
THERMODYNAMIC PROPERTIES:
Gibbs free energy G can be represented by G = U-Ts-M.B------------- (1)
Here U = internal energy
T = temperature
S = entropy
M = magnetic moment
B = magnetic induction
If we neglect volume changes and considering magnetic wave terms then dG = -M.dB.
From the above eq. we can derive the following equation
2
B
Gn − G s = c − − − − − − − − − − − − − − − − − − − −(2)
2 o
Here Gn and Gs refers to Gibbs free energy of the normal and the super conducting state, BC is the
critical magnetic field.
The above relation shows that in zero magnetic field the superconducting state is lower in
2
B
free energy by c per unit volume. This is shown in the fig
2 o

By using eqn. (2) we can estimate the critical field Bc (T) from the above graph.
The difference of entropies from eq. (2) as

GMS-58
 − Bc dBc
Sn − Ss = . − − − − − − − − − − − − − (3)
 o dT
dBc
Since the slope of the critical field curve is –ve, Sn > Ss revealing that the superconducting
dT
state is more ordered state than the normal state.
THERMAL CONDUCTIVITY:

The thermal conductivity of superconductors undergoes a continuous change between

two phases. This is usually lower in superconducting state as shown in the fig.

ENTROPY:

Entropy is a measure of dis-order in the system. The entropy of a superconductor

decreases rapidly on cooling below the transition temperature. This shows that superconducting
state is more ordered than the normal state. Below Tc, the entropy starts decreasing and the
electrons which were excited in normal state start ordering in superconducting state.

SPECIFIC HEAT:
At low temperatures the specific heat Cn of a normal metal is

GMS-59
given by Debye’s theory as C n = AT + BT 3 − − − − − − − − − − − (1)
The linear term AT is due to electronic excitations and the term T3 are due to lattice
vibrations. When the metal is in superconducting state the specific heat Cs will jump to a higher
value initially at Tc and then will slowly decrease and finally off quite below the value of normal
state indicating the existence of an energy gap. This is shown in the fig.
At very low temperature the specific heat falls below the normal state.
TYPE 1 AND TYPE 2 SUPERCONDUCTORS
On the basis of magnetic behavior, the superconductors are classified into the following
categories.
TYPE1 SUPERCONDUCTORS (or) SOFT SUPERCONDUCTORS
TYPE2 SUPERCONDUCTORS (or) HARD SUPERCONDUCTORS

GMS-60
TYPE1 SUPERCONDUCTORS:
A superconductor in which the transition from superconducting to normal state in presence of
magnetic field occurs sharply at the critical value Hc.
In the presence of external magnetic field H<Hc, type 1 superconductor in
superconducting state is a perfect dia magnet. When H exceeds Hc, the superconductor enters the
normal state and loses its diamagnetic property completely. In this state the magnetic flux
penetrates throughout the superconductor.
TYPE2 SUPERCONDUCTORS:
Type 2 superconductor characteristic curve contain two critical magnetic fields Hc1 and
Hc2 as shown in the fig

(1) For the field strength below Hc, superconductor expels magnetic field from its body
completely and behaves a perfect dia magnet. Hc1 is called the lower critical field. The curve is
represented by AB.
(2) As the magnetic field increases from Hc1, the magnetic field lines begin to penetrate the
material. The penetration increases until Hc2 is reached. Hc2 is called upper critical field. At Hc2
the external field has completely penetrated into superconductor and destroys the
superconductivity in the region Hc1and Hc2, the magnetic material is in a magnetically mixed
state but electrically it in a superconductor.
After Hc2 the material turns to normal state.
DEF: type 2 superconductors is one which is characterized by two electrical fields Hc1and Hc2
and transition to normal state takes place gradually as magnetic field is increased from Hc1to
Hc2.
APPLICATIONS OF SUPERCONDUCTORS:
(1) POWER APPLICATIONS:

If superconductors are used in power transition, the energy loss I2R will be eliminated
and power transmission can be done at lower voltage level.
(2) SUPER CONDUCTING MAGNETS:
An electromagnet made by using coils of superconducting wires is known as
superconducting magnets. The main advantage is that once the current is set up, the coil requires
no source of emf to drill the current. Superconducting magnets are used in magnetic resonance
imaging (MRI) technique. This technique is used to generate images of body cross-section. It is
much safer than using X-rays for the some study.
GMS-61
(3) ELECTRICAL APPLICATIONS: CRYOTRON:

It consists of a wire of superconducting material A around which another wire of

superconducting material B is wound in the form of solenoid as shown in the fig.
If a current is made to flow through Niobium wire B, then it will produce a magnetic field
around wire A. if this current is enough to produce magnetic field greater than Hc1 then
tantalum become a normal conductor. Hence A is switched to its
normal state and offers high resistance to the flow of current through tantalum. Now through A is
stopped.
By removing the current through niobium, the magnetic field around tantalum could be
brought below Hc. The current will again flow through A.
Hence it acts as fast acting switch.
(4) MAGLEV VEHICLES:
The maglev vehicles consist of superconducting magnets built into its base. Say the
vehicle runs over aluminum track in which a current is flowing. The train is set a float by
magnetic deviation. This is due to enormous repulsion between two highly powerful magnetic
fields, one produced by the superconducting magnet inside the train and the other due to electric
currents in the aluminum track. As a result the train floats without touching the track as repulsion
between superconducting magnets and the magnetic field induced in the track. A speed of 321
miles/hour was recorded in 1979 by a magnetic deviated train in Japan.
(5) VERY STRONG MAGNETIC FIELDS:
By using superconducting materials we can produce very strong magnetic fields.

GMS-62
 III B.Sc. Physics Paper IV (Modern Physics)
Problems and Answers

1. Energy of a particle at absolute temperature T is of the order of KT. Calculate the

wavelength of thermal neutrons at 27oC. Mass of neutron is 1.67×10-27 kg. Planck’s
constant h = 6.60×10-34 J-sec, Boltzmann constant K = 8.6×10-5 eV/deg.

Ans: Given T = 27 oC = 27+273 = 300 K

m= 1.67×10-27 kg
h = 6.60×10-34 J-sec
K = 8.6×10-5 eV/deg
h
Wavelength of particle  =
mv
h 2E
= (since v = )
2mE m
h
= (since energy of particle E = KT)
2mKT

Substituting the values of h, m, K and T in the above equation, we get

λ = 1.777 Ǻ

2. Calculate the wavelength associated with an electron having K.E. equal to 1.512
MeV. Rest mass energy is 0.512 MeV.

Ans: Given Kinetic energy K.E. = 1.512 MeV

Rest mass energy = moc2 = 0.512 MeV
mc2 = moc2 + K.E. (c = velocity of light = 3×108m/s)
= 0.512 + 1.512
= 2.024 MeV = 2.024×106×1.6×10-19 J (since 1eV = 1.6×10-19 J)
2.024 1.6 10−13
m = = 3.598 ×10-30 kg
(3 10 )
8 2

Rest mass mo = 0.512×106 / (3×108)2 = 4.608×10-10 kg

The speed of the electron is calculated from the equation
m0
m=
2
1− v 2
c
Substituting the values of m, mo and c in the above equation, we get
v = 2.902×108 m/s

Wavelength associated with the electron

h
= , where h = Planck’s constant = 6.60×10-34 J-sec
mv
Inserting the values of h, m and v, we get
wavelength λ = 0.00634 Ǻ

GMS-63
3. A nucleus is confined to nucleus of radius 5×10-15 m. Calculate the minimum
uncertainty in the momentum of the nucleon.

Ans: Given uncertainty in position = Δx = 5×10-15 m.

According to Heisenberg uncertainty relation
h
Δx.ΔPx ≈ , where h = Planck’s constant = 6.60×10-34 J-sec
2
Substituting the values of h and Δx, we get
Uncertainty in momentum ΔPx = 1.05×10-20kg-m/s

4. A microscope using photons is employed to locate an electron in an atom to within a

distance of 0.1 Ǻ. What is the uncertainty in velocity?

Ans: Given uncertainty in position = Δx = 0.1 Ǻ = 0.1×10-10 m.

According to Heisenberg uncertainty relation
Δx.ΔPx ≈ h , where h = Planck’s constant = 6.60×10-34 J-sec
Substituting the values of h and Δx, we get
Uncertainty in momentum ΔPx = m0.Δv
Mass of electron m0 = 9.1×10-31 kg
Therefore, Δx.m0Δv ≈ h ,
h 6.60 10−34
Δv = =
m0 x 9.110−31  0.110−10
= 7.28×107 m/s

5. Calculate the longest wavelength that can be analysed by rock salt crystal of spacing
2.82 Ǻ in the first order.

Ans: Given interplanar spacing d = 2.82 Ǻ.

According to Bragg’s law
n λ =2dsinθ
where, n = order of diffraction = 1 for first order
λ = wavelength
θ = Bragg’s angle
(sinθ)max = 1 , which means θmax = 90o
Substituting the values of d, n and θmax, we get λmax = 5.64 Ǻ

6. The radius of Ho165 is 7.731 fermi. Find the radius of He4.

Ans: Given radius of Ho165 r1 = 7.731 fermi

Mass number of Ho165 A1 = 165
Mass numbers and radii are related by the equation
1
r = r0 A 3
Let r2 be the radius and A2 be the mass number of He4

GMS-64
 Mass number of He4 A2 = 4
Then, r1 = roA11/3
r2 = roA21/3
r A 1
And 1 = ( 1 ) 3
r2 A2

Substituting the values of r1 , A1 and A2 in the above equation, we get

r2 = 2.238 fermi

7. X-rays of wavelength 1.54 Ǻ are diffracted by a crystal with first maximum

occurring at 11o. What is the separation between the lattice planes?

Ans: Given wavelength of X-rays λ = 1.54 Ǻ

Bragg’s angle θ = 11o
Order of diffraction n = 1
According to Bragg’s law, n λ =2dsinθ
Substituting the values of λ, θ and n, we get
Interplanar spacing d =4.035 Ǻ

8. A superconductor material has a critical temperature 3.7 K. Critical magnetic field

of 0.306 tesla at 0 K. Find the critical field at 2 K.

Ans: Given critical temperature Tc = 3.7 K

Critical field at 0 K Hc (0) = 0.306 tesla
At T = 2 K, the critical field is Given by
Hc (T) =Hc(0).[1-(T/Tc)2]
= 0.0306.[1-(2/3.7)2]
= 0.0217 tesla

9. If Kα-radiation of Mo (z = 42) has a wavelength of 0.75 Ǻ, calculate the

corresponding wavelength of radiation coming out of Co (z = 27).

Ans: Given atomic number of Mo = z1 = 42

Atomic number of Co = z2 = 27
Wavelength of Kα-radiation of Mo = λ1 = 0.75 Ǻ
Wavelengths and atomic numbers are related by the equation
1 ( z2 − 1)2
=
2 ( z 1 − 1)2
Substituting the values of z1, z2 and λ1 in the above equation, we get
Wavelength of radiation coming out of Co, λ2 = 1.865 Ǻ

10. The exciting line in an experiment is at 5460 Ǻ and the stokes line at 5520 Ǻ. Find the
wavelength of anti-stokes line.

GMS-65
Ans: Given wavelength of exciting line λ0 = 5460 Ǻ
Wavelength of stokes line λs = 5520 Ǻ
Let wave numbers of stokes, anti-stokes and exciting line are νs, νas and ν0
respectively. Let Δ ν be the Raman shift in wave numbers.
Wave number of anti-stokes line is Given by
νas = ν0 + Δ ν
where, Raman shift Δν = ν0 – νs

Therefore, νas = ν0 + ν0 – νs = 2 ν0 – νs
1 1
= 2× -
0 s
2 1
= -
5460 5520
2  5520 − 5460
=
5460  5520
1 5520  5460
Wavelength of anti-stokes line λas = = = 5401 Ǻ
 as 2  5520 − 5460

11. The wavelength of Hβ line is at 4861 Ǻ. Calculate the Rydberg constant.

Ans: Given wavelength of Hβ line λ = 4861 Ǻ

Wavelength and Rydberg constant for Hβ line are related by the equation
1 1 1 3
= R 2 − 2  = R
 2 4  16
Therefore, substituting the value of λ in the above equation, we get
Rydberg constant R = 1.097×107 m-1

12. What is the lowest energy that a neutron (mass = 1.67×10-27kg) can have if confined
to move along the edge of an impenetrable box of length 10-14 m? (h = 6.63×10-34J-S)

Ans: Given mass of neutron m = 1.67×10-27 kg

length of impenetrable box a = 10-14 m
Planck’s constant h = 6.63×10-34J-S
Energy of discrete energy levels in an impenetrable box is given by
n2h2
En =
8ma 2
For lowest energy level, n = 1
Substituting the values of n, h, m and a, we get

E1 = 3.29×10-13 J = 2.056 MeV

13. Find the binding energy of an α-particle from the following data:

GMS-66
 Mass of Proton = 1.007277 amu.
Mass of He nucleus = 4.001265 amu.
Mass of Neutron = 1.008666 amu.
Take 1 amu = 931.4 MeV.

Ans: Given Mass of Proton m p = 1.007277 amu.

Mass of He nucleus mHe = 4.001265 amu.
Mass of Neutron mn = 1.008666 amu.
In an Helium nucleus, there are 2 protons and 2 neutrons.
Therefore, mass defect in electron volts m = Binding energy (B.E.)
= ( 2m p + 2mn ) − mHe 
Substituting the values of m p , mHe , mn in the above equation, we get the value of
B.E. = 28.52 MeV

14. How many electrons, protons and neutrons are there in 14 grams of 6C14?
(Avogadro’s Number = 6.023×1023)

Ans: Given mass of 6C14 = 14 grams = 1 mole

Number of atoms present in 1 mole of a substance = Avogadro’s Number
= 6.023×1023

Therefore, number of atoms present in 14 grams of 6C14 = 6.023×1023

Number of protons in one 6C14 atom = atomic number = 6

Number of electrons in one 6C14 atom = 6
Number of neutrons in one 6C14 atom = 14 – 6 = 8

Therefore, number of protons in 14 grams of 6C14 atom = 6 × 6.023×1023

number of electrons in 14 grams of 6C14 atom = 6 × 6.023×1023
number of neutrons in 14 grams of 6C14 atom = 8 × 6.023×1023

15. How many kilowatt hours of energy will be released by the complete fission of 1
gram of U235? (Avogadro’s Number = 6.023×1023)

Ans: Given mass of U235 = 1gram

Mass number A = 235
Energy released in the fission = number of nuclei in 1 gram × energy released
per fission
1 6.023 1023
Therefore, energy released =  200 MeV
235
= 5.126× 1023 MeV
= 5.126× 1023 × 106×1.6×10-19 J (1eV = 1.6×10-19 J)
5.126  1023  106 1.6 10−19
=
3.6 106
GMS-67
 = 22.782×103 kWH

16. Electrons are accelerated to 344 volts and reflected from a crystal. The first
reflection maxima occurs, when glancing angle is 60o. Determine interplanar spacing
of the crystal.
h = 6.60×10-34 J-S
Electron charge e = 1.6×10-19 col.
Mass of electron = 9.1×10-31 kg

Ans: Given Acceleration voltage V = 344 V

Bragg angle θ = 60o
Mass of electron me= 9.1×10-31 kg
Planck’s constant h = 6.60×10-34 J-S

h
Wavelength of electrons  =
2me eV
Substituting the values of h, me, e, and V, we get the value of λ.
According to Bragg’s law
2dsinθ = nλ
Where, d = interplanar spacing
For first maxima n = 1
Substituting the values of θ, n and λ, we get
Interplanar spacing d = 0.381 Ǻ

17. What are the possible quantum numbers (s, l, j) of an atom in first two shells (n = 1, n
= 2)?

Ans: i) for shell n = 1,

l = 0, s = 1/2 and j = l ± s = 0 ± ½
=½
Therefore, possible values of (s, l, j) are (1/2, 0, 1/2)

ii) for shell n = 2

l = 0 and 1, s = 1/2 and j = l ± s = 0 ± 1/2 and 1 ± 1/2
= 1/2 and 3/2, ½ (three states are possible)
Therefore, the possible quantum numbers (s, l, j) are
(1/2, 0, 1/2), (1/2, 1, 3/2) and (1/2, 1, 1/2)

18. What is the Dowin-Haunt’s limit of X-ray tube working at 40 kV?

Ans: Given operation voltage = 40 kV = 40×103 V

hc
According to Dowin-Haunt’s law, min =
Ve
Where, h is Planck’s constant = 6.61×10-34 J-S
e = charge of electron = 1.6×10-19 c
GMS-68
 and c = velocity of light = 3×108 ms-1

12400 10−10 12400 10−10

Therefore, min = = = 310×10-13 m
V (volts) 40 103
= 0.310 Ǻ

19. Work function of Tungsten is 4.52 eV. Calculate the maximum wavelength of emitted
photoelectrons.

Ans: Given work function of Tungsten ω0 = 4.52 eV

hc
Work function ω0 = h 0 =
0
Where, ν0 is frequency, λ0 is wavelength of emitted photoelectron, c is
velocity of light and h is Planck’s constant.

Substituting the values of ω0, h and c, we get

λ0 = 2.747×10-7 m = 2747 Ǻ

20. Calculate the mass number (A) of a nucleus whose radius (R) is 2.72 fermi. (Given R0
= 1.2 fermi)

Ans: Given radius of the nucleus R = 2.72 fermi

R0 = 1.2 fermi
Let mass number be A.
Mass numbers and radii are related by the equation
1
R = R0 A 3
Substituting the values of R0 and R, we get mass number A = 12

21. Calculate the interplanar spacing for (111) plane in a simple cubic lattice where
lattice constant is 4×10-10 m.

Ans: Given the plane (h k l) = (111) i.e., h = 1, k = 1, l = 1

Lattice constant a = 4×10-10 m
The relation between lattice constant a and interplanar spacing d is given by
d
a=
h2 + k 2 + l 2
Substituting the values of a and (h k l), we get the interplanar spacing d = 4 3 Ǻ

22. The spacing between the planes of NaCl crystal is 2.81 Ǻ. It is found that the first-
order Bragg reflection occurs at angle of 10o. What is the wavelength of X-rays?

Ans: Given interplanar spacing d = 2.81 Ǻ

GMS-69
 Bragg’s angle θ = 10o
Order of diffraction n = 1 (first order)
According to Bragg’s law, n λ =2d sinθ
Substituting the values of d, θ and n, we get
Wavelength of X-rays λ = 0.976 Ǻ

23. Deduce the wavelength of Kα-line for an atom of z = 92. Given R = 1.1× 105 cm-1

Ans: For Kα-line,

1 3
= R( z − 1)2
K 4
Substituting the values of R and z, we get K = 0.1464×10-8 cm = 0.1464 Ǻ

24. In Uranium (z = 92), the K-absorption edge is 0.107 Ǻ and Kα line is 0.126 Ǻ.
Determine the wavelength of L-absorption edge.

Ans: Given λk = 0.107 Ǻ and K = 0.126 Ǻ

ch 12.4
EL = − =− keV = -115.9 keV
k 0.107
ch 12.4
And EL − EK = =− keV
K 0.126
 EL = −17.5 keV
ch 12.4
 L = = Ǻ = 0.709 Ǻ
EL 17.5

25. Calculate the rotational energy level of HCl molecule. Given bond length r = 1.3Ǻ

Ans: Given bond length r = 1.3Ǻ

The rotational energy is Given by,
h2
Er = 2 J ( J + 1) , where I is moment of inertia, J = rotational quantum
8 I
number and h is Planck’s constant.
h2
For J = 1, Er = 2  2
8 I
Moment of inertia I = Mr2, where M is the mass of HCl molecule.
M = MH + MCl = 1 + 35 = 36
2
2h
Hence, Er = 2 2
8 Mr
Substituting the values of Planck’s constant (h), mass M and radius r, we get the
desired value of energy.

GMS-70
26. The work function for sodium is 2.27 eV. What is the velocity of electrons emitted by
light of wavelength 4000 Ǻ. (Mass of electron is 9.1×10-31kg; h = 6.62×10-34J-S)

Ans: Given work function for sodium = 2.27 eV

Mass of electron is 9.1×10-31 kg
Planck’s constant h = 6.62×10-34 J-S

1
h = 0 + mv 2
2
We know that,
1 hc
 (h − 0 ) = mv 2 = − 0
2 
6.62 10−34  3 108
= − 2.27(1.6 10 −19 )
4000 10−10
= 1.333×10-19 J

2 1.33 10−19
v = −31
= 5.35 105 ms-1
9.110

27. The work function of Na is 2.3 eV. Does the sodium show photoelectric effect for
orange light with λ = 6800 Ǻ.

Ans: Given work function of Na = 2.3 eV

Wavelength of orange light λ = 6800 Ǻ
hc
Work function 0 = h 0 =
0
hc 6.626 10−34  3 108
 0 = =
0 2.3 1.6 10−19
Therefore, λ0 = 5400 Ǻ

This is the maximum wavelength, which can produce photoelectric emission from
sodium surface. But, the wavelength of Orange light is 6800 Ǻ (given). Hence, this
wavelength can not produce photoelectric effect from sodium surface.

28. Find the de-Broglie wavelength of a neutron whose energy is 12.8 MeV. Given mn =
1.675×10-27 kg

Ans: Given energy of neutron = 12.8 MeV

Mass of neutron mn = 1.675×10-27 kg
Kinetic energy K.E. = ½ mnv2 = 12.8 MeV = 12.8×1.6×10-19 J
 velocity v = 1.564 107 ms-1
h 6.625 10−34
De-Broglie wavelength  = =
mv (1.675 10−27 1.564 107 )
Therefore, λ = 2.529×10-20 m

GMS-71
29. An electron has a speed of 600 ms-1 with an accuracy of 0.005%. Calculate the
certainty with which we can locate the position of the electron.

Ans: Momentum of electron P = mv = 9.1×10-31× 600 kgms-1

 0.005  −5 −31
px =   mv = 5  10  9.1 10  600
 100 
px .x  h
h 6.6 10−34
x = = m
px 5 10−5  9.110−31  600
Δx = 0.02254 m

30. An electron is confined to a one dimensional potential box of width 1 Ǻ. Calculate the
first three energy levels.

Ans: The energy of a particle in an infinite one-dimensional potential well of width

‘a’ is Given by,
n2h2
En = , n = 1, 2, 3, …
8ma 2
(1) n = 1; a = 1 Ǻ = 10-10 m

En =
( 6.62 10 )
−34 2
 (1)2
8  9.1110−31  (10−10 )2
= 9.1  10-19 J
= 5.68 eV
(2) E2 = 4 E1 = 4 (5.68) = 22.7 eV
(3) E3 = 9 E1 = 9 (5.68) = 51.12 eV

31. A G.M. Counter collects 108 electrons/discharge. Counter rate is 500 counts/min.
What will be the average current in the circuit?

Ans: Counting rate = 500 counts/min

Total number of electrons collected in 1 min. = 500×108 = 5×1010
Therefore, Charge/min. = ne = 5×1010×1.6×10-19 = 8×10-9
Total charge per second = 8×10-9/60 = 1.33×10-10 A
Hence, average current in the circuit = 1.33×10-10 A

32. In a crystal, lattice plane cuts the intercepts 2a, 3b and 6c along the three axes. Find
the Miller indices of the given plane.

Ans: Here, pa: qb: rc = 2a: 3b: 6c

Where, a, b and c are primitive vectors of the unit cell
Therefore, p: q: r = 2: 3: 6

Taking reciprocals 1/p : 1/q : 1/r = 1/2 : 1/3: 1/6 = 3: 2: 1

GMS-72
Therefore, h : k : l = 3 : 2 : 1

Miller indices of the plane (h k l) = (3 2 1)

GMS-73