Atomic and

molecular
physics
16SCCPH6

III B.Sc., PHYSICS

 Atomic and molecular physics 16SCCPH6

ATOMIC AND MOLECULAR PHYSICS

Atomic physics is the field of physics that studies atoms as an isolated system of electrons and an
atomic nucleus. It is primarily concerned with the arrangement of electrons around the nucleus
and the nucleus and the process by which these arrangements change.
A smallest unit of element which consist of a dense, central positively charged nucleus
surrounded by negatively charged electron is called an atom
UNIT -I
CATHODE AND POSITIVE RAY ANALYSIS
1.1 PRODUCTION OF CATHODE RAYS
Gases at normal atmospheric pressure are poor conductors of electricity because they
do not have free electrons for conduction. But by special arrangement, one can make a gas to
conduct electricity. A simple and convenient device used to study the conduction of electricity
through gases is known as gas discharge tube. It consists of a long closed glass tube (of length
nearly50 cm and diameter of 4 cm) inside of which the gas in pure form is filled usually. The
small opening in the tube is connected to a high vacuum pump and a low-pressure gauge. This
tube is fitted with two metallic plates known as electrodes which are connected to secondary of
an induction coil. The electrode connected to positive of secondary is known as anode and the
electrode to the negative of the secondary is cathode. The potential of secondary is maintained
about 50 kV. Suppose the pressure of the gas in discharge tube is reduced to around 110 mm of
Hg using vacuum pump, it is observed that no discharge takes place. When the pressure is kept
near 100 mm of Hg, the discharge of electricity through the tube takes place. Consequently,
irregular streaks of light appear and also crackling sound is produced. When the pressure is
reduced to the order of 10 mm of Hg, a luminous column known as positive column is formed
from anode to cathode. When the pressure reaches to around 0.01 mm of Hg, positive column
disappears. At this time, a dark space is formed between anode and cathode which is often called
Crooke’s dark space and the walls of the tube appear with green color. At this stage, some
invisible rays emanate from cathode called cathode rays, which are later found be a beam of
electrons.

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1.2 PROPERTIES OF CATHODE RAYS

(1) Cathode rays possess energy and momentum and travel in a straight line with high speed of
the order of 107ms-1. It can be deflected by application of electric and magnetic fields. The
direction of deflection indicates that they are negatively charged particles.

(2) When the cathode rays are allowed to fall on matter, they produce heat. They affect the
photographic plates and also produce fluorescence when they fall on certain crystals and
minerals.
(3) When the cathode rays fall on a material of high atomic weight, x-rays are produced.
(4) Cathode rays ionize the gas through which they pass.
(5) The speed of cathode rays is up to of the speed of light.

1.3 MILLIKAN’S OIL DROP EXPERIMENT: DETERMINATION OF CHARGE OF

AN ELECTRON

Principle: This method is based on the study of the motion of uncharged oil drop under free fall
due to gravity and charged oil drop in a uniform electric field. By adjusting uniform electric field
suitably, a charged oil drop can be made to move up or down even kept balanced in the field of
view for sufficiently long time and a series of observation can be made.

Experimental arrangement: The apparatus consists of two horizontal circular metal plates A
and B, about 22 cm in diameter and separated by a distance of about 16mm as shown in figure.
The upper plate has a hole (H) in the middle. These plates are held together by insulating rods of
glass or ebonite, so that they are perfectly parallel to each other. The plates are surrounded by a
constant temperature bath D and the chamber C containing dry air. The plates are connected to a
battery which can provide a potential difference of the order of 10000V.

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Theory: A spray of fine droplets of a highly viscous liquid (such as glycerin) is produced by
means of an atomizer (AT) near the hole H and enter the space between A and B. The droplets
are illuminated by an arc lamp L and are seen through a microscope whose eyepiece is provided
with micrometer scale. One such droplet is viewed through the microscope as it descends under
gravity. The viscous force due to air increases and soon it attains a constant terminal velocity and
let it be v. the terminal velocity v of the droplet is measured using the microscope.
i) Motion under gravity :The gravitational force acting on the oil drop downwards is equal to
4 3
mg= 3πa ρg,
Where a is the radius of the oil drop,
ρ is the density of the oil and
g the acceleration due to gravity.
The up thrust experienced by the oil drop due to displaced air is 4πa3σg
3
Where σ is the density of air.
The net downward force acting on the oil drop=
Weight of the oil drop-up thrust experienced by the oil drop
4 4
= πa3ρg − πa3σg
3 3
= 4 πa3(ρ – σ)g -------------- (1)
3
Since the oil drop attains a terminal velocity v, the net downward force acting on the oil drop is
equal to the viscous force acting opposite to the direction of motion of the oil drop.
By Stoke’s law the viscous force on the oil drop is 6πaηv,
Where η is the coefficient of viscosity of air.
4
3
πa 3 (ρ – σ) g=6πaηv ------------------------- ( 2)
The radius of the oil drop is
9𝜂𝑣
a= ( 2(ρ – σ)g )½ ------- (3)

ii) Motion under electric field : The air inside the parallel plate is ionized by sending a
beam of X-rays .The droplets pickup one or more electrons from the ionized air. Let q be the
charge carried by the droplet under observation. Let E be the electric field applied between the
plates A and B, so the drop moves upward with terminal velocity v1, which can be determined
using the microscope. The force on droplet due to electric field is Eq. Since the velocity of the
droplet is uniform, we have
4
Eq= πa3(ρ – σ)g+6πaηv1
3
4
Eq - πa3(ρ – σ)g= 6πaηv1 ........................... (4)
3
Adding equation (2) and (4)
Eq=6πaη (v+v1) ------------------------ (5)
Substituting the value of a in equation (5) from equation (3)
9𝑣
Eq=6πaη3/2(v+v1)( )½ ------ (6)
2(ρ – σ)g
If V is the potential difference between A and B, d is the distance between them
E=V/d

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Millikan determined the value q for a large number of oil drops using equation (6) and found that
they are an integral multiple of a least value. The greatest common factor gives the charge e of
the electron. The charge of an electron was found to be 1.602×10-19C

1.4 DISCOVERY OF POSITIVE RAYS:

If the cathode in a discharge tube is perforated, "luminous rays" are observed behind the
cathode. These rays travel in a direction opposite to the cathode rays, i.e. from anode to the
cathode. These rays produce fluorescence rays when they strike a fluorescent screen present at
the back of the cathode. They are deflected by electric and magnetic fields. The direction of
deflection of these rays is opposite to that of cathode rays. This shows that they are positively
charged. These rays are called positive rays or canal rays.

1.5 PROPERTIES OF POSITIVE RAYS

1. Positive rays consist of positively charged particles.
2. The nature of these rays depends on the gas used in the discharge tube.
3. These rays travel in straight lines.
4. These rays get deflected by an electrical field, and bend towards the negative plate. Thus the
deflection of the positive rays is in a direction opposite to that shown by the cathode rays.
5. These rays are also deflected by the magnetic fields in the direction opposite to that of the
cathode rays.
6. These rays can produce mechanical as well as chemical effects.
7. The ratio of charge (e) to mass (m), i.e.,(e/m) for the particles in the positive rays is not the
same for all gases.
8. The ratio e / m for the positive rays is very low as compared to the e / m value for cathode
rays.
9. These rays affect a photographic plate, produce fluorescence and penetrate thin aluminium
foils
10. The velocities of all the positive ray particles is not the same. The velocities of these rays
range from 10 to:100 ms-1

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1.6 POSITIVE RAY ANALYSIS-THOMSON 'S PARABOLA METHOD:

Thomson determined the charge to mass ratio of positive ions .It consists of a discharge tube (A)
in which the pressure of the gas is about 10-5m of mercury. The anode is held in a side tube. In
order to ensure the supply of the gas under test, a steady Stream of the gas is allowed to flow in
through a capillary tube (E) and after circulating in A is pumped off at F. The cathode (C) is
perforated with an extremely fine hole. The cathode is cooled by the water jacket (J). The
positive ions produced in A fly towards the cathode and those reaching it axially pass straight
through the fine hole and emerge from the opposite end of the cathode as a narrow beam. This
beam is then subjected to parallel electric and magnetic fields simultaneously. An electric field is
applied between the plates P and Q. The electric field is perpendicular to the positive ray beam.
N and S are the poles of a strong electromagnet. After passing through these fields, the beam
enters a highly evacuated camera G and is received on a photographic plate R. A liquid air-trap
(T) helps to keep the pressure in G quite low, even though pressure in A is comparatively large.
The photographic plate, when developed, shows a series of parabola.

Theory: Consider a positive ion of mass M, charge E and velocity v. When no electric or
magnetic field is applied, the positive ion strikes the screen at O. This is called the undeflected
spot.
Action of Electric Field: Let an electric field of strength X act over a length l of the path of the
ion. 1 XE 𝑙
Displacement of the ion in Passing through the electric field s = 2 ( M ) ( ) ²
v
After leaving the field, the ion moves in a straight line and finally strikes the plate at a
distance x from O. x is proportional to s as well as to the distance between the field and the plate.
Hence

𝑋𝐸 𝑙² 𝑋𝐸
𝑥 ∝ 2M v² or 𝑥 =k1 M v² .............(1)

Here k1 is a constant.

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Action of Magnetic Field: Suppose a magnetic field of strength B is applied over the same
length 𝑙 in the same direction as that of the electric field. The positive ion will now be deflected
by this field in a direction at right angles to that in which it was deflected by the electric field. It
will strike the plate at a distance y from O such that oy is perpendicular to ox in the plane of the
plate.
Displacement of the ion just emerging from the magnetic field
1 BEv 𝑙 ² = 1 BE𝑙²
s′ = (
2 M) (v) 2 Mv

On emerging from the field, the ion moves in a straight line and finally strikes the plate at a
distance y from O. y is proportional to s′ as well as to the distance between the field and the
plate.

Hence,
1 BE𝑙² BE
y∝ 2 Mv or y=k2 Mv ....................... (2)
Here k2 is another constant.
Action of Combined Electric and Magnetic Fields The combined effect of the two fields is
found by eliminating v from (1) and (2).
Squaring (2) and dividing by (1),
𝑦² 𝑘₂² 𝐵² 𝐸
𝑥
=(𝑘₁² )M …..(3)
𝑦²
B and X are constants. If E/M is constant, then by Eq. (3),
𝑥 = constant. This is the equation of
a parabola. As Eq. (3) is independent of v, particles of same E/M but of different velocities will
fall on different points on the same parabola.
𝑦 𝑘₂ 𝐵 𝑦
= v i.e.,
𝑥∝
𝑥 𝑘₁ 𝑋
v

Thus, the position of any individual particle on the parabola will depend on the velocity of the
particle. The ions having different values of E/M will lie along the different parabolas. For one
direction of the magnetic field, one half of the parabola is traced. Reversing the magnetic field,
the other half is also traced. When the full parabola is traced, it is easy to draw the axis of
symmetry (X-axis)
Determination of E/M: The value of E/M can be calculated from Eq. (3) by measuring the
coordinates x and y for a point on the parabola, evaluating the constants k1, and k2 for the
apparatus and knowing B and X.

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Determination of Mass: The mass of a positive ion is determined in terms of mass M1 of the
standard hydrogen ion. A small trace of hydrogen is always present in all samples of gases.
Hydrogen, being the lightest element, gives the outermost parabola. Let I and II represent the
parabolic traces due to ions of the gas of mass M2 and the hydrogen ions of mass M1
respectively. An ordinate abcde is drawn It cuts the two parabolas at a, b, d, e and the x axis at c .
let ac and bc represent the two values of y corresponding to a constant value of x on these
parabolas. Let us assume that both ions have the same charge. Then from eq. (3)

𝑎𝑐² 𝑘₂² 𝐵² 𝐸
𝑥
=( 𝑘₁ 𝑋 ) M₁
𝑏𝑐² 𝑘₂² ² 𝐸
𝑥
=( 𝑘₁ 𝑋
) M₂
M2 𝑎𝑐² 𝑎𝑒
= = ( )²
𝑀1 𝑏𝑐² 𝑏𝑑
The length ae and bd can be measured on the photograph. Hence the parabolic tracesenable us to
compare the masses of different ions with hydrogen used as a standard
𝑒
2 =( )
M ²M ---- (4)
1
𝑏𝑑
Discovery of stable isotopes:
Using neon gas in his apparatus, Thomson obtained two parabolas for the gas itself, one
corresponding to a mass 20 and a much weaker one corresponding to a mass 22. The
intensity ratio of the two traces was 9:1 which gave the relative abundance of the two
isotopes. Thomson therefore suggested that neon could exist in the form of two isotopes,
chemically indistinguishable but with different masses 20 and 22. The actual observed atomic
weight (20.2) of neon is the weighted mean of the masses of these two isotopes.
Limitations of the Parabola Method:
1. Due to the velocity dispersion, each parabolic is of very low intensity.
2. The traces on the photographic plate are blurred and have no definite edges. Hence accurate
measurements are not possible.
3. The influence of secondary rays makes analysis difficult.

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 Atomic and molecular physics 16SCCPH6

1.7 ASTON'S MASS SPECTROGRAPH:

The stream of positive ions obtained from a discharge tube is rendered into a fine beam by
passing it between two narrow slits s1 and s2. This beam enters the electric field between the
metal plates P1 and P2. Due to the action of the electric field (X), all positive ions having the
same value of E/M are not only deviated by an angle 𝜃 from the original path but are dispersed
by an angle d𝜃 due to their different velocities. The beam is then allowed to pass through a
magnetic field M acting at right angles to the electric field so that it produces a deflection of the
beam in the same plane. The magnetic field deviates the particles by an angle ϕ and reconverges
them by dϕ. The direction and magnitude of the field is so adjusted that it produces a deviation of
the beam in the opposite direction and brings all ions having the same value of E/M, even though
differing in velocities, to a focus at one point F. Ions having different values of E/M are brought
to focus at different points on the photographic plate. The condition required for such a focusing
may be derived as follows

Theory:
To obtain the condition of focusing: Consider a group of ions having the same value of E/M, but
moving with different velocities. Let 𝜃 and ϕ be the mean angles of deviation of the group of
ions in the electric and magnetic fields respectively. Let d be the dispersion angle due to the
electric field and dϕ the convergence angle due to the magnetic field.
i) let X= The strength of the electric field,
E=charge of the ion
M= Mass of the ion
v= velocity of the ion

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 Atomic and molecular physics 16SCCPH6

l1= length of the electric field

d1= the linear displacement
then
1 XE 𝑙₁ ²
d1 =
2 M ( v)
𝑑₁ 1 XE 𝑙₁
The angular deviation of the beam = 𝜃= 𝑙₁
= 2 M v²
----- (1)
XE 𝑙₁
Angle of dispersion of the beam d𝜃 = - M v³
dv -------- (2)
dθ 2dv
=- ----- (3)
θ v

ii) Similarly if d 2 =displacement of an ion from its path due to magnetic

field of strength and l 2 = the length path of the ion in the magnetic field

1 Bev 𝑙₂ ²
d2 =
2 M
( v)
The deviation produced by the magnetic field in the opposite direction
ϕ = 𝑑₂ =
1 BE 𝑙₂
𝑙₂ 2 M v
----- (4)
1 BE 𝑙₂ ------ (5)
dϕ =
2 M v²
dϕ dv
= - ------ (6)
ϕ v

dθ 2dϕ
= - ϕ
θ
dϕ ϕ
= 2θ
------- (7)
dθ
Let a=OR = the distance between the two fields. The width of the selected group of ions at
R=adθ. If there had been no magnetic field, the width of the group after travelling a further
distance b would be (a + b) dθ . The magnetic field produces a convergence dϕ and brings
group of ions to a focus at a distance RF=b

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The condition of focusing is given by

ϕ ϕ
(a+b) d𝜃=b dϕ or a+b= d =
b dθ 2θ
b 2θ ------ (8)
a
= ϕ −2 θ

This expression represents a straight line drawn from o, making an angle 2𝜃 with the direction of
the beam deviated by the electric field. If ϕ = 2 θ , the rays do not converge (sine b=infinity).
However if ϕ = 4 θ, b= a and the convergent beam can be easily photographed. The ions are
focused at F such that OR=RF.
Detection of isotopes:
To determine the masses of isotopes of an element, the element is mixed with a number
of other elements whose atomic masses are known accurately. The traces all of them are obtained
on the same photographic plate. The distances of the traces of the known masses are measured
from a given reference point on the plate. A calibration graph is drawn connecting the distances
with the atomic masses. By measuring the distances of the traces of the isotopes of the element
from the same reference point, their atomic masses are obtained from calibration graph.
Advantages:
1. All the particles having the same value of E/M are focused at a Single point unlike
Thomson's method in which they are spread out into a parabola. Hence, the intensities of
the lines on the photographic plate in Aston's mass spectrograph are large, while the
parabolic traces photographic plate in Thomson's arrangement are feeble.

2. The intensity of a line in the mass spectrum is proportional to the number of particles of
that mass. Hence a rough idea of the relative abundance of various isotopes of an element
can be made by this method.
Limitations:
1. The mass scale is not linear.
2. Owing to the polarization of the electrodes of the electric field, the traces are not quite
Straight but slightly curved.

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 Atomic and molecular physics 16SCCPH6

1.8 BAINBRIDGE’S MASS SPECTROGRAPH

The beam of positive ions produced in a discharge tube is collimated by two slits S1 and
S2 and enter a velocity selector. The velocity selector consists of
i ) a steady electric field X maintained at right angles to the ion beam between two plane
parallel plates P1 and P2 and
ii) A magnetic field B.
The magnetic field is produced by an electromagnet represented by the dotted circle. The
magnetic field B is perpendicular to x and the ion beam. The electric field and magnetic field of
the velocity sector are so adjusted that the deflection produced by one is nullified by the
deflection produced by the other. If X and B are the electric intensity and magnetic induction
then Xe = Bev or v=X/B.

Only those ions having the velocity v, alone pass through the entry slit S3 to enter the
evacuated chamber D, thus all ions entering D must have the same velocity. The positive ions
which entered into D are subjected to a strong uniform magnetic field of intensity B’
perpendicular to its path. The force acting on each ion will be B'ev. Ions with different masses
trace circular paths of different radii given by
Mv
R= (B'ev= Mv )
𝐵′𝑒 𝑅
e v
=
𝑀 θ

Since v and B' are constant quantities,

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After describing semicircles, the ions strike a photographic plate.

B’eR
Now M= .If e is the same for all ions, then M=R.
𝑣
So we get a linear mass scale on the photographic plate. It will be seen that ions of different
masses strike the photographic plate at different points, thus giving a typical mass spectrum.
Advantages:
i) Since a linear mass scale is obtained, accuracy of measurements is increased.
ii) The sensitivity depends on the strength of the deflecting magnetic field B’ and the
field area of the chamber D, Bainbridge used a magnetic field of 1.5 weber/m2 over a
semicircle of radius 0.2 m. he found a definite increase in resolving power over
Aston’s apparatus. The ten isotopes of tin were resolved by the instruments

1.9 DEMPSTER’S MASS SPECTROGRAPH

In experimental arrangement the anode is a metal cylinder A with its front surface C
coated with a salt of the element under test and heated electrically. The filament, if electrically
heated by the battery B1, emits electrons. By maintaining the filament at a P.D of about 50 volts
with respect to A by using another battery B2. The electrons are made to bombard the heated salt
with the result that the anode emits positively charged ions of the element. These ions are
collimated into a narrow beam by the slit S1. Then the positive ions are accelerated towards the
slit S2 by a variable P.D V maintained between S1 and S2 . We know that when ions of mass M
and charge e are accelerated through a P.D V they acquire a velocity v is given by

1 2 = √2𝑒𝑉
2 Mv =eV or v M -------------------------------(1)

The velocity of the ions v is very large compared with their initial speeds of emission. The ions
then enter a vacuum chamber G. On entering the space G , the ions are subjected to a magnetic
field of flux density B directed at right angles to the plane of the diagram. The ions are deflected
through a semicircle ‘s towards the slit S4 defined by three slits S2,S3 S4,. The magnetic field of

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 Atomic and molecular physics 16SCCPH6

flux density B makes an ion of mass M entering with the velocity v traverse a circular path of
radius r is given by
𝑀𝑣² 𝑀𝑣
Bev = r or r = Be ------------- (2)
But , from(1), v=(2eV/M)1/2
𝑀𝑣 𝑀
r = Be =Be (2eV/M)1/2 =(2MV/B2e)1/2
2𝑀𝑣
r2= B²e
𝑒 2𝑣
=
M B²r² -----------------------------
( 3)

For this particular value of V, only ions with the specific charge given by equation (3)are
collected by the electrode p and the registered by the electrometer E.
𝑀 𝑉
From the equation r =(2MV/B2e)1/2 , it is clear that if ( ) is kept constant,the
e B²
radius r of the path of these ions will remain unchanged. Hence ions of different e/M can be
made to traverse a circular path of fixed radius by adjusting V and B.
Determination of the masses of the isotopes:
In the actual experiment, the magnetic field (B) is kept constant and the ionic current is
measured by the electrometer for various values of V. A graph is plotted with this current against
V. the graph will show sharp peaks at those values of v corresponding to the value of M given by
Eq.(3). Figure gives the curve for potassium, showing the two isotopes of mass numbers 39
and41. The relative abundance of the isotopes can be inferred from the relative heights of the
peaks.

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 Atomic and molecular physics 16SCCPH6

1.10 MASS DEFECT AND PACKING FRACTION

Mass defect of a given isotope is defined as the difference between the experimentally
measured mass of the isotopes(M) and its mass number(A).
Mass defect=∆= M-A
The packing fraction of the isotope is defined as the ratio of its mass defect (M-A) to its
Mass number (A)
Packing fraction = (M-A)/A

BINDING ENERGY:
When Z protons and N neutrons combine to make a nucleus, some of the mass (∆m)
disappears because it is converted into an amount of energy ∆E=(∆m)c2. This is called the
binding energy(B.E)of the nucleus.
B.E=(Zmp+Nmn)c2-Mnc2

Where mp=mass of the proton

mn=mass of the neutron
Mn=nuclear mass

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