B.Sc.

V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
Physics, Semester-V
DSC 6: Elements of Atomic, Molecular & Laser Physics
Unit 1: Basic Atomic Model
Thomson’s atomic model; Rutherford atomic model – Model, Theory of alpha particle scattering, Rutherford
scattering formula; Bohr atomic model – postulates, Derivation of expression for radius, total energy of
electron; Origin of the spectral lines; Spectral series of hydrogen atom; Effect of nuclear motion on atomic
spectra - derivation; Ritz combination principle; Correspondence principle; Critical potentials – critical
potential, excitation potential and ionisation potential; Atomic excitation and its types, Franck-Hertz
experiment; Sommerfeld’s atomic model – model, Derivation of condition for allowed elliptical orbits.

Basic Atomic Model

Thompson Atomic Model:

An atom is the smallest particle of a chemical element possessing the chemical

properties of the element. The first model of an atom was given by J. J.

Thomson in 1904. According to Thomson, an atom is a positive sphere of

radius 0.53 Å, in which the mass and charge are uniformly distributed. The

electrons are embedded in the positively charged sphere just like the plums in

a pudding or the seeds in fruits like watermelon, which will give maximum stability to the atoms. Further, the

number of positive charges in an atom is equal to the number of negative charges which explains the electrical

neutrality of the atom. However, this model could not explain (i) the origin of spectral lines in the hydrogen

atom (ii) the large angle of scattering of alpha particles. (iii) All features of optical spectra of hydrogen and

other elements.

Rutherford’s Experiments on Scattering of 𝜶-particles:

In 1911, Rutherford performed a
number of experiments on the
scattering of α-particles by a very thin
gold foil The experimental
arrangement is shown in Fig. α-
particles are emitted by some
radioactive material (polonium) R, kept
inside a thick lead box. D is the lead
screen with a small hole in it to select a very fine beam of α-particles. This well collimated beam is then
allowed to fall on a thin gold foil F. While passing through the gold foil, the α-particles are scattered through
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
different angles. A zinc sulphide screen was placed on the other side of the gold foil. This screen was movable,
so as to receive the α-particles, scattered from the gold foil at angles varying from 0 to 180°. When a α-particle
strikes the screen, it produces a flash of light and it is observed by the microscope M. It was found that:
(1) Most of the α-particles passed through the gold foil with small deviation.
(2) There were a few particles that were scattered through large angles. Experimental results showed that one
of about 8000 particles suffered angles of scattering > 90°. A few of the α-particles were even scattered directly
in the backward direction (i.e., angle of scattering = 180°). Thomson’s atom model failed to explain the
experimental results. Therefore, Rutherford pictured an atom as follows.
Rutherford Nuclear Atom Model:
(1) The atom has a small, positively charged nucleus (dimensions of the order of 10−14 m). All positive charges
of an atom and most of the mass of the atom are concentrated in the nucleus. Electrons have no place inside
the nucleus. The electrons revolve around this nucleus at some distance away. The dimensions of the nucleus
and of the electrons are negligibly small as compared to the overall size of the atom, so that most of the volume
occupied by an atom is actually an empty space. Thus, the discovery of the nucleus of the atom is due to
Rutherford.
(2) Since the electron-distribution must give stability to the atom, the electrons could not be stationary. The
electrons must be revolving around the nucleus in closed orbits, so that the centrifugal force due to the rotation
of the electron is balanced by the force of electrostatic attraction between the nucleus and the electrons. Thus,
Rutherford proposed a dynamic planetary model in which nucleus plays the role of the sun and electrons
correspond to the individual planets of the solar system. Since most of the atom is empty, most of the α-
particles pass through the foil without appreciable deflection. However, if a α-particle is moving in such a
direction so as to have a head-on collision with the nucleus, the α-particle will be scattered through large
angles. Sometimes, when a head-on collision occurs, the α-particle is turned back. Thus, the Rutherford’s
model of the nucleus enables us to account for very large deviations.
Theory of α-particle Scattering:
We shall assume the following:
(1) The α-particle and the nucleus are point charges.
(2) The scattering is due to coulomb electrostatic repulsive forces between the α-particle and the positive
charge of the nucleus (Ze).
(3) The nucleus is so massive compared with the α-particle that it does not move during their interaction.
(4) The α-particles do not penetrate the nuclear region and the strong interaction nuclear forces are not
involved.
(5) Let r be the instantaneous separation between α-particle and nucleus. Owing to the variation of the electric
1
force with 𝑟 2, the α-particle’s path is a hyperbola with the nucleus at the outer focus.
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
Definitions:
(1) The impact parameter b: The impact parameter is defined as the perpendicular distance of the velocity
vector of the 𝛼- particle from the centre of the nucleus, when it is far away from the atom.
(2) The Scattering angle 𝜃 is the angle between the asymptotic direction of approach of the α-particle and
the asymptotic direction in which it recedes.
Expression for Impact Parameter (Relationship between b and θ):

Let 𝑃1 𝑎𝑛𝑑 𝑃2 be the linear momentum

of the 𝛼 particle when it is far from the
nucleus before and after the interaction
respectively. As the 𝛼 particle not
colliding with the nucleus and
deviating from the nucleus, the
magnitudes of 𝑃1 𝑎𝑛𝑑 𝑃2 are same
only the direction changes. Therefore, the change in momentum is

𝑑𝑡
∆𝑃 = 𝑃2 − 𝑃1 = ∫ 𝐹. 𝑐𝑜𝑠𝜑. 𝑑𝑡 = ∫ 𝐹. 𝑐𝑜𝑠𝜑. . 𝑑𝜑 … … … . (1)
𝑑𝜑

From figure,

∆𝑃 𝑚𝑣
= Sine Rule
𝑠𝑖𝑛𝜃 𝑠𝑖𝑛 1 (𝜋 − 𝜃)
2

𝑚𝑣 𝑠𝑖𝑛𝜃
∆𝑃 =
1
𝑠𝑖𝑛 2 (𝜋 − 𝜃)

𝜃 𝜃 𝜋 𝜃 𝜃 𝜃
𝑚𝑣 2 𝑠𝑖𝑛 2 . 𝑐𝑜𝑠 2 sin ( − ) = 𝑠𝑖𝑛 (90 − ) = 𝑐𝑜𝑠
∆𝑃 = 2 2 2 2
𝜃
𝑐𝑜𝑠 2

𝜃
∆𝑃 = 2 𝑚𝑣 𝑠𝑖𝑛 … … … (2)
2

The central force or electrostatic force of repulsion is given by

1 2𝑒. 𝑍𝑒 2𝑍𝑒 2
𝐹= . 2 = … … … (3) Charge on Alpha Particle=2e
4𝜋𝜖𝑜 𝑟 4𝜋𝜖𝑜 𝑟 2

The electric force exerted by the nucleus on the 𝛼 particle acts along the radius vector joining them. So, there
is no torque (𝜏 = 𝑟 × 𝐹 = 𝑟𝐹𝑠𝑖𝑛𝜃, 𝜃𝑖𝑠 𝑡ℎ𝑒 𝑎𝑛𝑔𝑙𝑒 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝑟 𝑎𝑛𝑑 𝐹, 𝜃 = 0; ∴ 𝜏 = 0) on the 𝛼 particle and
its angular momentum is constant. Hence,
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
𝑑𝜑
𝑚𝑟 2 𝜔 = 𝑚𝑟 2 = 𝑎 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 𝑚𝑣𝑏 𝐿 = 𝑟 × 𝑃 = 𝑏 × 𝑚𝑣
𝑑𝑡

𝑑𝜑 𝑣𝑏
= 2
𝑑𝑡 𝑟

𝑑𝑡 𝑟2
= … … . . (4)
𝑑𝜑 𝑣𝑏

𝑑𝑡
Substituting the values of ∆𝑃, 𝐹 𝑎𝑛𝑑 from equation 2, 3 & 4 in equation 1, we get
𝑑𝜑

𝜋−𝜃
2
𝜃 2𝑍𝑒 2 𝑟 2
2 𝑚𝑣 𝑠𝑖𝑛 = ∫ . . 𝑐𝑜𝑠𝜑. 𝑑𝜑
2 4𝜋𝜖𝑜 𝑟 2 𝑣𝑏
𝜋−𝜃
−
2

𝜋−𝜃
𝜃 2𝑍𝑒 2 𝑟 2 2
2 𝑚𝑣 𝑠𝑖𝑛 = . (𝑠𝑖𝑛𝜑) 𝜋−𝜃
2 4𝜋𝜖𝑜 𝑟 2 𝑣𝑏 −
2

𝜃
𝑍𝑒 2 2 𝑐𝑜𝑠 2
𝑏= .
4𝜋𝜖𝑜 𝑚𝑣 2 𝑠𝑖𝑛 𝜃
2

𝑍𝑒 2 𝜃 1
𝑏= . 2 𝑐𝑜𝑡 𝐾 = 𝑚𝑣 2
4𝜋𝜖𝑜 2 𝐾 2 2

𝒁𝒆𝟐 𝜽
𝒃= . 𝒄𝒐𝒕
𝟒𝝅𝝐𝒐 𝑲 𝟐

This is the relation between the impact parameter b and the scattering angle θ. The scattering angle θ decreases
with increasing impact parameter. 𝑏 in terms of D (distance of closest approach)
𝐷 𝜃
𝑏= . 𝑐𝑜𝑡
2 2

Rutherford Scattering formula:

All α-particles that approach the nucleus with an impact
parameter ≤ 𝑏 will be scattered by an angle ≥ 𝜃. The
area around each nucleus (Figure) with a radius equal to
an impact parameter 𝑏 is called the integral cross section.
This area is
𝜎 = 𝜋𝑏 2 … … . (1)
Consider a gold foil with a surface area A and a thickness
t. If 𝑛 is the No. of nuclei per unit volume, the foil will
contain 𝑛𝐴𝑡 nuclei. Therefore, the target area 𝑇 offered by those nuclei in order to have scattering angles
greater than 𝜃 and impact parameter less than 𝑏 will be
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
𝑇 = 𝑛𝐴𝑡𝜎 … … … . (2)
Since 𝐴 is the total target area, the fraction of α-particles experiencing scattering angles greater than 𝜃 will be
𝑡𝑎𝑟𝑔𝑒𝑡 𝑎𝑟𝑒𝑎 𝑜𝑓𝑓𝑒𝑟𝑒𝑑 𝑏𝑦 𝑛𝑢𝑐𝑙𝑒𝑖 𝑖𝑛 𝑡ℎ𝑒 𝑓𝑜𝑖𝑙 𝑛𝐴𝑡𝜎
𝑓 = =
𝑡𝑜𝑡𝑎𝑙 𝑡𝑎𝑟𝑔𝑒𝑡 𝑎𝑟𝑒𝑎 𝐴

𝑓 = 𝑛 𝑡 𝜎 = 𝑛 𝑡 𝜋 𝑏 2 … … . . (3)
𝑍𝑒 2 𝜃
Substituting, 𝑏 = . 𝑐𝑜𝑡 in eq (3)
4𝜋𝜖𝑜 𝐾 2

2
𝑍𝑒 2 𝜃
𝑓 =𝑛𝑡𝜋 ( ) 𝑐𝑜𝑡 2 … … . . (4)
4𝜋𝜖𝑜 𝐾 2
In an actual experiment, a detector measures α-particles scattered between 𝜃 𝑎𝑛𝑑 𝜃 + 𝑑𝜃. The fraction of
incident α-particles so scattered is found by differentiating Eq.
(4) with respect to 𝜃.
2
𝑍𝑒 2 𝜃 𝜃
𝑑𝑓 = − 𝑛 𝑡 𝜋 ( ) 𝑐𝑜𝑡 . 𝑐𝑜𝑠𝑒𝑐 2
4𝜋𝜖𝑜 𝐾 2 2
In the experiment, a fluorescent screen was placed at a distance
r from the foil. The scattered α-particles were detected by
means of the scintillations they caused. Those α-particles
scattered between 𝜃 𝑎𝑛𝑑 𝜃 + 𝑑𝜃 reached a zone of a sphere of
radius 𝑟 whose width is 𝑟 𝑑𝜃. The zone radius = 𝑟 𝑠𝑖𝑛 𝜃. So,
the area of the screen struck by these particles is
𝑑𝑠 = (2 𝜋 𝑟 𝑠𝑖𝑛𝜃)(𝑟 𝑑𝜃) = 2 𝜋 𝑟 2 𝑠𝑖𝑛𝜃 𝑑𝜃
𝜃 𝜃
𝑑𝑠 = 4 𝜋 𝑟 2 sin cos 𝑑𝜃
2 2
Let 𝑁𝑖 be the total number of α-particles directed against the target. Then the No. scattered into 𝑑𝜃 𝑎𝑡 𝜃 =
𝑁𝑖 𝑑𝑓.
No. of particles per unit area striking the screen at 𝜃 is
2
𝑍𝑒 2 𝜃 2𝜃
𝑁 𝑛 𝑡 𝜋 ( )
𝑁𝑖 ⌊𝑑𝑓⌋ 𝑖 4𝜋𝜖𝑜 𝐾 𝑐𝑜𝑡 2 . 𝑐𝑜𝑠𝑒𝑐 2 𝑑𝜃
𝑁(𝜃) = =
𝑑𝑠 𝜃 𝜃
4 𝜋 𝑟 2 sin 2 cos 2 𝑑𝜃

𝑵𝒊 𝒏 𝒕 𝒁𝟐 𝒆𝟒
𝑵(𝜽) =
𝜽
(𝟖𝝅𝝐𝒐 )𝟐 𝒓𝟐 𝑲𝟐 𝒔𝒊𝒏𝟒 ( )
𝟐

The above equation is called the Rutherford Scattering formula.

𝜃
Note: 𝐷𝑖𝑓𝑓𝑒𝑟𝑒𝑛𝑡𝑖𝑎𝑡𝑒 𝑐𝑜𝑡 2 2 𝑤𝑖𝑡ℎ𝑟𝑒𝑠𝑝𝑒𝑐𝑡 𝑡𝑜 𝜃.

𝜃 𝜃
𝑇𝑎𝑘𝑒, 𝑦 = 𝑐𝑜𝑡 2 ; 𝑙𝑒𝑡 𝑢 =
2 2
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
𝑦 = 𝑐𝑜𝑡 2 𝑢

𝑑𝑦 𝑑𝑦 𝑑𝑢
= .
𝑑𝜃 𝑑𝑢 𝑑𝜃

𝑑𝑦 𝑑
= 2 𝑐𝑜𝑡𝑢. (𝑐𝑜𝑡𝑢)
𝑑𝑢 𝑑𝑢
𝑑𝑦
= − 2 𝑐𝑜𝑡𝑢. 𝑐𝑜𝑠𝑒𝑐 2 𝑢 𝐷𝑖𝑓𝑓𝑟𝑒𝑛𝑡𝑖𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑐𝑜𝑡𝑢 𝑖𝑠(− 𝑐𝑜𝑠𝑒𝑐2 𝑢 )
𝑑𝑢
𝑑𝑢 𝑑 𝜃 1
= ( )=
𝑑𝜃 𝑑𝜃 2 2
𝒅𝒚
= − 𝒄𝒐𝒕𝒖. 𝒄𝒐𝒔𝒆𝒄𝟐 𝒖
𝒅𝜽

Bohr Atom Model

Bohr assumed basically Rutherford nuclear-model of the atom and tried to overcome the defects of the model.
He proposed the following two postulates. Bohr’s atom model is introduced in the year 1913.
Basic Postulates:
(1) An electron cannot revolve round the nucleus in all possible orbits as suggested by the classical theory.
The electron can revolve round the nucleus only in those allowed or permissible orbits for which the angular
momentum of the electron is an integral multiple of h/2π.
Here, h is the Planck’s constant = 6.64 × 10−34 𝐽𝑠. These orbits are called stationary orbits and an electron
revolving in these orbits does not radiate energy.
(For an electron of mass m, moving with a speed v in an orbit of radius r, 𝐿 = 𝑚𝑣𝑟 = 𝑚𝑟 2 𝜔 = 𝑛ℎ/2𝜋. n
is called the Principal quantum number. It takes integral values, excluding zero; n = 1, 2, 3, 4 .......)
(2) An atom radiates energy only when an electron jumps from a stationary orbit of higher energy to one of
lower energy. If the electron jumps from an initial orbit of energy 𝐸𝑖 to a final orbit of energy 𝐸𝑓 (𝐸𝑖 > 𝐸𝑓 ),
𝐸𝑖 −𝐸𝑓
a photon of frequency 𝜈 = is emitted.
ℎ

The Bohr formulae:

Based on these postulates, Bohr derived the formulae for (i) the radii of the stationary
orbits and (ii) the total energy of the electron in the orbit. Consider an atom whose
nucleus has a positive charge Ze and mass M (Fig). For hydrogen, Z = 1. Let an
electron of charge (–e) and mass m move round the nucleus in an orbit of radius r.
Since M >> m, the nucleus is stationary. Hence the mass of the nucleus does not come
into the calculations.
The electrostatic force of attraction between the nucleus and the electron is
1 𝑍𝑒. 𝑒
4 𝜋 𝜖0 𝑟 2
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
𝑚𝑣 2
The centrifugal force on the electron =
𝑟
The system will be stable if
𝑚𝑣 2 1 𝑍𝑒. 𝑒
= … … … . . (1)
𝑟 4 𝜋 𝜖0 𝑟 2
According to Bohr’s first postulate,
𝑛ℎ 𝑛ℎ
𝑚𝑣𝑟 = 𝑜𝑟 𝑣 =
2𝜋 2𝜋𝑚𝑟
2
𝑛2 ℎ2
𝑣 = … … … … (2)
4 𝜋 2 𝑚2 𝑟 2
Substituting this value of 𝑣 2 in (1),
𝑚 𝑛2 ℎ2 1 𝑍𝑒 2
. =
𝑟 4 𝜋 2 𝑚 2 𝑟 2 4 𝜋 𝜖0 𝑟 2
𝑛 2 ℎ 2 𝜖0
𝑟= … … … . . (3)
𝜋 𝑍𝑒 2 𝑚
Therefore, radius of the 𝑛𝑡ℎ permissible orbit for hydrogen is
𝑛 2 ℎ 2 𝜖0
𝑟𝑛 = ∵𝑍=1
𝜋 𝑒2𝑚
From equation (5) we find that 𝑟𝑛 ∝ 𝑛2 . The radii of the orbits are in the ratio of 1: 4:9:16: 25 etc. The radius
of the first orbit for hydrogen atom 𝑟1 = 0.053 nm.This is called the Bohr radius.
Calculation of total energy: The total energy of the electron in any orbit is the sum of its kinetic and potential
energies. The potential energy of the electron is considered to be zero when it is at an infinite distance from
the nucleus. P.E. of an electron in an orbit is given by the work done in bringing the electron from infinity to
that orbit. This amount of work is obtained by integrating the electrostatic force of attraction between the
nucleus and the electron from the limits ∞ to r.
𝑟
𝑍𝑒 2 −𝑍𝑒 2
𝑃. 𝐸. 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 = ∫ 𝑑𝑟 = … … … … (4)
4𝜋𝜖0 𝑟 2 4 𝜋 𝜖0 𝑟
∞

1 2
𝑍𝑒 2
𝐾. 𝐸. 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 = 𝑚𝑣 = … … … … (5) 𝑓𝑟𝑜𝑚 (1)
2 8 𝜋 𝜖0 𝑟
Total energy of the electron in the nth orbit is
𝐸𝑛 = 𝑃. 𝐸 + 𝐾. 𝐸
−𝑍𝑒 2 𝑍𝑒 2 −𝑍𝑒 2
𝐸𝑛 = + =
4 𝜋 𝜖0 𝑟 8 𝜋 𝜖 0 𝑟 8 𝜋 𝜖0 𝑟
Substituting the value of r from (3),
−𝑍𝑒 2 𝜋 𝑍 𝑒 2 𝑚
𝐸𝑛 = .
8 𝜋 𝜖0 𝑛 2 ℎ 2 𝜖0
−𝑚 𝑒 4 𝑍 2
𝐸𝑛 = … … … . (6)
8 𝜖0 2 𝑛 2 ℎ 2
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
As the value of n increases, 𝐸𝑛 increases. Hence, the outer orbits have greater energies than the inner orbits.
Bohr’s interpretation of the Hydrogen spectrum:
If an electron jumps from an outer initial orbit 𝑛2 of higher energy to an inner orbit 𝑛1 of lower energy, the
frequency of the radiation emitted is given by
𝐸𝑛2 − 𝐸𝑛1
𝜈=
ℎ
−𝑚 𝑒 4 1
𝐸𝑛2 = 2 2
. 2
8 𝜖0 ℎ 𝑛2
−𝑚 𝑒 4 1
𝐸𝑛1 = .
8 𝜖0 2 ℎ2 𝑛1 2
𝑚 𝑒4 1 1
𝜈= 2 3
{ 2 − 2}
8 𝜖0 ℎ 𝑛1 𝑛2
The wavenumber 𝜈 of a radiation is defined as the reciprocal of its wavelength λ in vacuum and gives the
1 𝜈
number of waves contained in unit length in vacuum. 𝜈 = 𝜆 = 𝑐
4
𝑚𝑒 1 1
𝜈= { − }
8 𝜖0 2 𝑐 ℎ3 𝑛1 2 𝑛2 2
𝑚 𝑒4
= 𝑅 is known as Rydberg constant.
8 𝜖0 2 𝑐 ℎ 3

Spectral series of hydrogen atom

(1) Lyman series.
When an electron jumps from second, third, ... etc., orbits to the first
orbit, we get the Lyman series which lies in the ultraviolet region.
Here, 𝑛1 = 1 and 𝑛2 = 2, 3, 4, 5 . . ..
1 1
𝜈 = 𝑅{ 2
− 2}
1 𝑛2
(2) Balmer series.
When an electron jumps from outer orbits to the second orbit, 𝑛1 = 2 and 𝑛2 = 3, 4, 5 . . ..etc.
1 1
𝜈 = 𝑅{ 2
− 2}
2 𝑛2
This series is called Balmer series and lies in the visible region of the spectrum. The first line in the series
(𝑛2 = 3) is called the 𝐻𝛼 line, the second (𝑛2 = 4) the 𝐻𝛽 line and so on.
(3) Paschen series.
Paschen series in the infrared region are given by 𝑛1 = 3 and 𝑛2 = 4, 5, 6 . . ..etc.
1 1
𝜈 = 𝑅{ 2
− 2}
3 𝑛2
(4) Brackett series. If 𝑛1 = 4 and 𝑛2 = 5, 6, 7 . . ..etc., we get the Brackett series.
1 1
𝜈 = 𝑅{ − }
42 𝑛2 2
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
(5) Pfund series. If 𝑛1 = 5 and 𝑛2 = 6, 7, 8 . . ..etc., we get Pfund series.
Effect of finite nuclear mass on atomic spectra:

In Bohr Theory, we have assumed that the nucleus remains fixed at the centre of the circular orbit
while the electron revolves round it. This is true if the nucleus has infinite mass. If the nucleus has a mass M,
both the nucleus and orbital electron revolve around a common centre of mass with same angular velocity𝜔.
Let N and e represent the nucleus and the electron of mass M and m respectively. Now both of them are
rotating about their common centre of mass C, the nucleus moving in
circle of radius r1 and the electron in a circle of radius r2. Let r represent
the distance between the nucleus and electron. Then according to centre
of mass theory, we have
𝑀𝑟1 = 𝑚𝑟2

𝑆𝑖𝑛𝑐𝑒 𝑟 = 𝑟1 + 𝑟2

𝑀𝑟1
𝑟 = 𝑟1 +
𝑚

𝑀
𝑟 = 𝑟1 (1 + )
𝑚

𝑚+𝑀
𝑟 = 𝑟1 ( )
𝑚
𝑚𝑟
𝑟1 =
𝑚+𝑀
𝑀𝑟
Similarly, 𝑟2 = 𝑚+𝑀

The total angular momentum of the atom about the centre of mass is

𝐿 = 𝑀𝑟12 𝜔 + 𝑚𝑟22 𝜔

Substituting the values of 𝑟1 &𝑟2 , we get

𝑚𝑟 2 𝑀𝑟 2
𝐿 = 𝑀( ) 𝜔+𝑚( ) 𝜔
𝑚+𝑀 𝑚+𝑀

𝑀𝑚2 2
𝑚𝑀2
𝐿= 𝑟 𝜔 + 𝑟 2𝜔
(𝑚 + 𝑀)2 (𝑚 + 𝑀)2

𝑚𝑀
𝐿= (𝑚 + 𝑀)𝑟 2 𝜔
(𝑚 + 𝑀)2

𝑚𝑀 2
𝐿= 𝑟 𝜔
𝑚+𝑀

𝐿 = 𝜇𝑟 2 𝜔
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
𝑚𝑀
Where, 𝜇 = 𝑚+𝑀 is called the reduced mass of the electron. According Bohr’s first postulate,

𝑛ℎ
𝜇𝑟 2 𝜔 =
2𝜋

In the absence of nuclear motion, the corresponding equation was

𝑛ℎ
𝑚𝑟 2 𝜔 =
2𝜋

The above two equations are similar, except the m has been replaced by𝜇. Therefore, to take into
account the finite mass of the nucleus we must replace the mass of the electron (m) in all the Bohr formulae
by the reduced mass (𝜇). Therefore, the equation for the frequency of the spectral lines of the atom is given
by

𝜇𝑒 4 𝑍 2 1 1
𝜈= 2 3 ( 2 − 2)
8𝜖0 ℎ 𝑛1 𝑛2

Ritz combination principle:

Statement: By a combination of the terms that occur in the Rydberg or Balmer formula, other relations can
be obtained holding good for new lines and new series.
By this principle, Ritz predicted new series of lines in the hydrogen spectrum before they were actually
discovered.
Consider the first two lines, 𝐻𝛼 and 𝐻𝛽 of the Balmer series. We may represent them
1 1 1 1
𝜈𝛼 = 𝑅 { 2
− 2 } 𝑎𝑛𝑑 𝜈𝛽 = 𝑅 { 2 − 2 }
2 3 2 4
Combining these two formulae,
1 1
𝜈𝛽 − 𝜈𝛼 = 𝑅 { − }
32 42

This represents a new line. It is the first line of a new series in the infrared, discovered by Paschen. Similarly,
the second line of the Paschen series can be obtained by forming the difference of 𝐻𝛾 and 𝐻𝛼 and so on.
Correspondence Principle:
In 1932 Niels Bohr proposed a correspondence principle.
Statement: Any new theory in Physics must reduce to well-established corresponding classical theory when
the new theory is applied to the special situation in which the less general theory is known to be valid.
Explanation: Bohr’s theory gives only the frequencies of the spectral lines and says nothing about the nature
(whether polarised or not) and intensity of lines, whereas classical theory is very successful in this respect.
Also, according to classical theory, the frequency of the spectral line is the same as the orbital frequency of
the electron (𝜈 = 𝜔/2𝜋). But in Bohr’s theory, the frequency of the spectral line is determined by the
difference in energy between two orbital states: 𝜈 = (𝐸𝑖 − 𝐸𝑓 )/ℎ. But it can be shown that, for transitions
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
between states whose quantum numbers are relatively high, the frequency of the spectral line coincides very
nearly with the orbital frequency.
Let us consider an atom of effectively infinite mass. Then
−𝑚 𝑒 4
𝐸𝑛 =
8 𝜖0 2 𝑛 2 ℎ 2
If n is sufficiently great, the energy change ∆E corresponding to a change of n by ∆n is obtained by
differentiating equation (1).
𝑚 𝑒4
∆𝐸𝑛 = ∆𝑛
4 𝜖0 2 𝑛 3 ℎ 2
∆𝐸𝑛 𝑚 𝑒4
𝜈= = ∆𝑛
ℎ 4 𝜖0 2 𝑛 3 ℎ 3
According to Bohr’s first postulate,
𝑛ℎ
= 𝑚 𝑟2 𝜔
2𝜋
𝑛ℎ = 2 𝜋 𝑚 𝑟 2 𝜔
𝑚 𝑒4
𝜈= ∆𝑛
4 𝜖0 2 (2 𝜋 𝑚 𝑟 2 𝜔)3
𝑚 𝑒4
𝜈= ∆𝑛
32 𝜖0 2 𝜋 3 𝑚3 𝑟 6 𝜔 3
Now for the equilibrium in the orbit, we have,
1 𝑒2 1 4𝜋 𝜖0 𝑚 𝜔2
𝑚𝑟𝜔2 = . 2 𝑜𝑟 3 =
4𝜋 𝜖0 𝑟 𝑟 𝑒2
2
𝑚 𝑒4 4𝜋 𝜖0 𝑚 𝜔2
𝜈= . ( ) ∆𝑛
32 𝜖0 2 𝜋 3 𝑚3 𝜔 3 𝑒2
𝜔
𝜈= ∆𝑛
2𝜋
Now if, ∆𝑛 = 1, then,
𝜔
𝜈=
2𝜋
Thus, the frequency given by the quantum theory for two very large quantum numbers and separated by unity
becomes identical with the orbital frequency and hence with the classical frequency. Therefore, we may
conclude that the behaviour of the atom tends asymptotically to that expected from the classical theory in the
region of large quantum numbers. This correspondence principle has proved to be of great value in the
computation of the intensity, polarisation and coherence of spectral radiation, as well as in the formulation of
the so-called selection rules.
Critical Potential:

‘The least energy, expressed in electron volts, required to excite a free neutral atom from its ground
state to higher state is called a critical potential of the atom’.
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
There are two kinds of critical potentials, namely, excitation potential and ionization potential.

Excitation potential: The energy in electron volts required to raise an atom from its normal state to an excited
state is called excitation potential of the state.

Ionization potential: The energy required to remove an electron from a given orbit to an infinite distance
from the nucleus.

Atomic Excitation:
There are two main ways of exciting an atom.
(i) Excitation by Collision. One method of exciting the atoms is to bombard them with electrons having
enough kinetic energy. To produce a luminous discharge in a rarefied gas, an electric field is established that
accelerates electrons until their kinetic energies are sufficient to excite atoms they collide with. The electron
gives up all or part of its energy in exciting the atom. The atom then emits a photon in returning to its ground
state. Neon signs and mercury vapour lamps are familiar examples of how a strong electric field applied
between electrodes in a gas-filled tube leads to the emission of the characteristic spectral radiation of that gas.
We get reddish light in the case of neon and bluish light in the case of mercury vapour.
(ii) Irradiation of atoms with light. Atoms can be excited by energy supplied in the form of light. An atom
absorbs a photon of light whose energy is just the right amount to raise the atom to a higher energy level. For
example, a photon of wavelength 121.7 nm is emitted when a hydrogen atom in the n = 2 state drops to the n
= 1 state. Absorbing a photon of wavelength 121.7 nm by a hydrogen atom initially in the n = 1 state will
therefore bring it up to the n = 2 state. This process explains the origin of absorption spectra. When white
light, which contains all wavelengths, is passed through hydrogen gas, photons of those wavelengths that
correspond to transitions between energy levels are absorbed. The resulting excited hydrogen atoms radiate
their excitation energy almost at once. But these photons come off in random directions with only a few in the
same direction as the original beam of white light. The dark lines in an absorption spectrum are therefore never
completely black, but only appear so by contrast with the bright background. We expect the absorption
spectrum of any element to be identical with its emission spectrum and this agrees with observations. For
example, in the case of sodium, the two black absorption lines occupy exactly the same position in the
spectrum as the two yellow D1 and D2 emission lines.
Experimental determination of critical potentials by Frank and Hertz’s method:
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
The gas of the element under study (Hg vapour) is filled in a glass tube (T) at a pressure of about 1
mm of mercury [fig 1]. Electrons are produced by heating the filament (F) by a low-tension battery (B). These
electrons are accelerated towards a grid G by the potential difference V between F and G. V can be varied
between 0 and 60 volts. P is the collector plate which is kept at a slightly negative potential by 𝑉 ′ about 0.5V,
with respect to G. Thus, only those electrons from G can go to P which have kinetic energies greater than this
potential difference. The milliammeter measures the plate current.

Keeping 𝑉 ′ constant, 𝑉 is gradually increased in small steps from zero onwards. A plot of the collector
current against the accelerating potential V is shown in Fig 2. From this graph, we see that there is no collector
current for V less than 0.5 volts. Above this, the collector current increases continuously. When the
accelerating potential difference reaches a value 4.9 volts, the current suddenly dips to a minimum. Again,
when the potential difference is gradually increased above 4.9 volts, the current gradually increases till another
maximum is reached when the potential difference is just below 9.8 volts. At 9.8 volts, the current again dips
steeply to a minimum. Similarly, a significant decrease in the collector current occurs each time the
accelerating potential is increased by approximately 5 volts.

Explanation of the graph:

Consider the case of a beam of slow electrons travelling through mercury vapour at low pressure. If
the electrons suffer no energy loss due to collision with the atoms of the gas, they will reach the collector plate.
On increasing the accelerating potential, collector current increase. As V reaches the value of a critical
potential 4.9 volts, an electron acquires 4.9 eV of energy on reaching G. The electron loses all its energy in an
inelastic collision with a mercury atom. Thus, the electron is left with no energy to reach P, consequently the
collector current drops abruptly. This suggests that the Hg (Mercury) atoms has absorbed this 4.9 eV energy
to raise it from the ground state to a state of higher energy.

This current dipping to a minimum at 4.9 volts does not reach zero because statistically some electrons
may succeed in reaching the collector plate, avoiding an inelastic collision with a mercury atom. Such
electrons record minimum current on the plate. Then as V is further increased, the electrons start reaching P
after the inelastic collisions, if they are left with energy to overcome 𝑉 ′ . Hence, the plate current again
increases. At 𝑉 = 9.8 volts, the current again dips to a second minimum. This can be explained if an electron
of 9.8 𝑒𝑉 energy suffers two consecutive inelastic collisions with different mercury atoms before it reaches
the plate. Such an electron excites both the mercury atoms to their first excited states, losing 4.9 𝑒𝑉 energy in
each collision. This explains the second minimum.

Each time the excited atoms, while returning to the ground state emits a photon of wavelength
2536 A0. Thus, one can show mathematically the energy of a photon of this wavelength is 4.9 eV

ℎ𝑐 6.63 × 10−34 × 3 × 108

𝐸 = ℎ𝜈 = = = 4.9 𝑒𝑉
𝜆 2536 × 10−10 × 1.602 × 10−19
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
This experiment shows in a very convincing way the existence of discrete energy levels in the mercury atom.
The main drawback of this experiment is that one cannot distinguish between the excitation and ionization
potentials.

Sommerfeld’s Relativistic Atom Model:

Introduction: According to Bohr, the lines in the hydrogen spectrum should each have a well-defined
wavelength. Spectrographs of high resolving power showed that the 𝐻𝛼 , 𝐻𝛽 , 𝑎𝑛𝑑 𝐻𝛾 lines in the hydrogen
spectrum are not single. Each spectral line actually consisted of several very close lines packed together.
Michelson found that under high resolution, the 𝐻𝛼 line can be resolved into two close components, with a
wavelength separation of 0.13 Å. This is called the fine structure of the spectral lines. Bohr’s theory could not
explain this fine structure.
To explain the observed fine structure of spectral lines, Sommerfeld introduced two main modifications in
Bohr’s theory.
(1) According to Sommerfeld, the path of an electron around the nucleus, in general, is an ellipse with the
nucleus at one of the foci. The circular orbits of Bohr are a special case of this.
(2) The velocity of the electron moving in an elliptical orbit varies considerably at different parts of the orbit.
This causes relativistic variation in the mass of the moving electron. Therefore, he took into account the
relativistic variation of the mass of the electron with velocity. Hence this is known as the relativistic atom-
model.
Elliptic orbits for hydrogen: Consider the electron moving in an elliptical orbit round the nucleus (N). Its
position at any instant can be fixed in terms of polar coordinates r and φ (Figure). In the case of circular orbits,
there is only one coordinate that varies periodically, namely, the angle φ that the radius vector makes with the
X-axis. In the case of elliptic motion, not only does the angle φ vary but the length of the radius vector r also
varies periodically, as shown in the above figure. We have now to quantise the momenta associated with both
these coordinates (φ and r) in accordance with Bohr’s quantum condition. The two quantisation conditions
are,

∫ 𝑃𝜙 𝑑𝜙 = 𝑛𝜙 ℎ … … … . . (1)

∫ 𝑃𝑟 𝑑𝑟 = 𝑛𝑟 ℎ … … … . . (2)

𝑛𝜙 is called the angular or azimuthal quantum number and 𝑛𝑟 is

called the radial quantum number. 𝑛𝜙 and 𝑛𝑟 take only positive
integral values and 𝑛𝜙 + 𝑛𝑟 = 𝑛, where n is the principal quantum
number. It can take the integral values 1, 2, 3, .... etc.
To determine the allowed elliptical orbits, we have to evaluate the integrals in equation (1) and (2). The
momentum 𝑃𝜙 corresponding to the coordinate φ is merely the angular momentum p of the electron in the
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
elliptic orbit and this, from Kepler’s law, is a constant, i.e., 𝑃𝜙 = 𝑝 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡. Integrating equation (1)
from 0 𝑡𝑜 2𝜋,
2𝜋

∫ 𝑃𝜙 𝑑𝜙 = 𝑛𝜙 ℎ
0

𝑃𝜙 (2𝜋 − 0) = 𝑛𝜙 ℎ
𝑛𝜙 ℎ
𝑃𝜙 = … … … . (3)
2𝜋
Evaluation of ∫ 𝑷𝒓 𝒅𝒓 = 𝒏𝒓 𝒉
𝑑𝑟 𝑑𝑟
Now, momentum along the radius 𝑃𝑟 = 𝑚. 𝑝 = 𝑚𝑣 = 𝑚
𝑑𝑡
𝑑𝑡

𝑑𝑟 𝑑𝑟 𝑑𝜙 𝑑𝑟 𝑑𝑟 2 𝑑𝜙
𝑃𝑟 𝑑𝑟 = 𝑚. 𝑑𝑟 = 𝑚 ( . ) . 𝑑𝜙 = 𝑚. ( ) . 𝑑𝜙
𝑑𝑡 𝑑𝜙 𝑑𝑡 𝑑𝜙 𝑑𝜙 𝑑𝑡
But,
𝑑𝜙 𝑑𝜙
𝑃𝜙 = 𝑚𝑟 2 𝐴𝑛𝑔𝑢𝑙𝑎𝑟 𝑀𝑜𝑚𝑒𝑛𝑡𝑢𝑚 = 𝑚𝑟 2 𝜔 = 𝑚𝑟 2
𝑑𝑡
𝑑𝑡
1 𝑑𝑟 2
𝑃𝑟 𝑑𝑟 = ( . ) 𝑃𝜙 . 𝑑𝜙 … … … … . (4)
𝑟 𝑑𝜙
The equation of an ellipse in polar coordinates is
1 1 + 𝜀 𝑐𝑜𝑠𝜙
= … … … … . (5)
𝑟 𝑎(1 − 𝜀 2 )
where a is the semimajor axis and ε is the eccentricity. Taking logarithm of Eqn. (5) and differentiating,
1 𝑑𝑟 𝜀 sin 𝜙
. =
𝑟 𝑑𝜙 1 + 𝜀 cos 𝜙
𝜀 2 𝑠𝑖𝑛2 𝜙
∴ 𝑃𝑟 𝑑𝑟 = . 𝑃 . 𝑑𝜙
(1 + 𝜀 cos 𝜙)2 𝜙
Eqn. (2) now becomes
2𝜋
𝜀 2 𝑠𝑖𝑛2 𝜙
𝑃𝜙 ∫ 𝑑𝜙 = 𝑛𝑟 ℎ … … … . (6)
(1 + 𝜀 cos 𝜙)2
0
Integrating the LHS of the above integration by parts, we get,
2𝜋
𝜀2 𝑠𝑖𝑛2 𝜙 2𝜋
∫ 𝑑𝜙 = − 2𝜋
(1 + 𝜀 cos 𝜙)2 (1 − 𝜀2 )1/2
0
Thus, Equation (6) becomes
2𝜋 𝑃𝜙
− 2𝜋 𝑃𝜙 = 𝑛𝑟 ℎ
(1 − 𝜀 2 )1/2
Substituting the value of 𝑃𝜙 from equation (3), we have,
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli
𝑛𝜙 ℎ
− 𝑛𝜙 ℎ = 𝑛𝑟 ℎ
(1 − 𝜀 2 )1/2
𝑛𝜙
𝑛𝑟 = − 𝑛𝜙
(1 − 𝜀 2 )1/2
𝑛𝜙
𝑛𝑟 + 𝑛𝜙 =
(1 − 𝜀 2 )1/2
But, 𝑛𝑟 + 𝑛𝜙 = 𝑛, the principal quantum number. Hence,
𝑛𝜙
𝑛=
(1 − 𝜀 2 )1/2
𝑛𝜙
(1 − 𝜀 2 )1/2 =
𝑛
𝑛𝜙 2
1 − 𝜀2 =
𝑛2
𝑏2
For an ellipse 1 − 𝜀 2 = 𝑎2 , where a and b are the semi-major and semi-minor axes respectively. Hence,

𝑏 2 𝑛𝜙 2
= 2
𝑎2 𝑛
𝑏 𝑛𝜙
= … … . . (7)
𝑎 𝑛
Equation (7) is the condition that determines the allowed elliptical orbits. When 𝑛𝜙 = 𝑛, 𝑏 = 𝑎, 𝜀 = 0 and
the orbit becomes circular. 𝑛𝜙 cannot be zero, since the ellipse would then degenerate into a straight line
passing through the nucleus. Also, 𝑛𝜙 cannot be greater than 𝑛, since b is always less than a. Hence for a
given value of 𝑛, 𝑛𝜙 can assume only n different values, which means there can be only 𝑛 elliptical orbits of
different eccentricities.
Example:
1. For the first orbit 𝑛 = 1
𝑛 = 𝑛𝑟 + 𝑛𝜙 = 1
𝑎𝑠 𝑛𝜙 ≠ 0, 𝑛 = 𝑛𝜙 = 1 ⇒ 𝑛 = 𝑛𝜙
𝐹𝑜𝑟 𝑛 = 𝑛𝜙 , the only allowed orbit is 𝐶𝑖𝑟𝑐𝑙𝑒.
2. For second orbit 𝑛 = 2
With 𝑛 = 2, 𝑛𝜙 may have the values 1 or 2, so that there are two possible orbits, a circle and an ellipse.
3. For third orbit 𝑛 = 3
With 𝑛 = 3, 𝑛𝜙 may have the values 1, 2 or 3, so that there are three possible orbits, a circle and two
ellipses.
B.Sc. V Semester (P-6) Elements of Atomic, Molecular & Laser Physics A D B F G College, H Halli

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