Paper 601 - Unit 1 : Atomic Physics

Review of Bohr’s theory of hydrogen atom

Introduction : Atomic physics deals with atom as an isolated system of electrons and an
atomic nucleus. It is primarily concerned with the arrangement of electrons around the
nucleus and the processes by which these arrangements change. An atom is the smallest
particle of an element that has the properties characterizing that element. One of the first
breakthroughs in the study of an atom was achieved by Sir Ernest Rutherford in 1911. He
established that the mass of the atom is concentrated in its nucleus. He also proposed that
the nucleus has a positive charge and is surrounded by negatively charged electrons. The
existence of electrons was already discovered in 1897 by J. J. Thomson. This theory of
atomic structure was complemented by Niels Bohr in 1913 who explained the origin of
spectral lines of hydrogen atom. Bohr proposed the following postulates.

Postulates of Bohr’s theory

(1) In an atom the electrons move in circular orbits with the nucleus at its centre. As
long as electrons revolve in these orbits, they do not emit radiation (energy). These
orbits are called the stationary orbits.
(2) Electrons can revolve in only those specific stationary orbits for which the orbital
angular momentum of the electron about the nucleus is an integral multiple of ℏ (ℏ
= h/2). Thus an electron in the nth orbit will have an angular momentum (𝐿 =
𝑚𝑣𝑟) given by 𝒎𝒗𝒓 = 𝒏ℏ where n = 1,2,3,…m the mass, v the velocity of the
electron and r the radius of the orbit.
(3) When an electron jumps from one stationary orbit of higher energy to another orbit
of lower energy, it radiates the excess energy as a quantum, corresponding to which
a spectral line is emitted. If 𝐸𝑖 and 𝐸𝑓 are the energies of an electron in the two orbits,
then 𝑬𝒇 − 𝑬𝒊 = 𝒉𝝂.
Using the Bohr’s postulates, the expressions for the radius of the electron orbit, energy of
the electron and the wavelength of the emitted spectral line can be obtained.

(1) Expression for radius of an electron orbit: Consider an atom of atomic number
Z, with charge on the nucleus as Ze. Let m be the mass and 𝜐 the linear velocity of the
electron. Let the radius of the electron orbit be r. The electrostatic force provides the
necessary centripetal force that keeps the electron in the orbit.
mv 2 1 Ze 2 Ze 2
Thus = …(1) or mv 2 r = …..(2)
r 4 0 r 2 4 0
nh n2h2
From the Bohr’s quantization rule mvr = …..(3) or m 2 v 2 r 2 = …..(4)
2 4 2
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 Paper 601 - Unit 1 : Atomic Physics

m 2 v 2 r 2 n 2 h 2 4 0 n 2 h 2 0
Dividing (4) by (2) =  This gives r = . The radius of the Bohr
mv 2 r 4 2 Ze 2  m Ze2
orbit is directly proportional to the square of the quantum number n.
(2) Expression for orbital velocity of the electron : From the Bohr’s quantization
nh n 2 h 2 0
rule mvr = ….(1) where r = ….(2)
2  mZe2
 n 2 h 2 0  nh Ze2
Equation (2) in (1) gives mv  2 
= or v =
  m Ze  2 2n h  0
From the above equation v is found to be inversely proportional to n which shows that
velocity of an electron in the outer orbit is less than that in the inner orbit.
(3) Expression for energy of the electron: The total energy (E) of an electron in an
orbit is the sum of its potential energy (EP) and kinetic energy (EK) where
Ze 2 1
EP = − ….(1) and EK = mv 2 …(2)
4 0 r 2
mv 2 1 Ze2 1 Ze2
From the Bohr’s postulate = or mv2 = …(3)
r 4 0 r 2 4 0 r
1 Ze 2
Substituting for mv2 from (3) in (2) we get E K =  …..(4) .
2 4 0 r
Total energy of the electron in the nth Bohr orbit is E = EP + EK
Ze 2 1 Ze 2 Ze 2  1 Ze 2 Ze 2
or E= − +  or E = − 1 + = − . Thus 𝐸 = −
4 0 r  2 
𝑛
4 0 r 2 4 0 r 8 0 r 8 0 r
n 2 h 2 0 mZ 2e4 13.6Z
2
As r = we get En = − 2 2 2 J or E = − eV (for H – atom, Z =1)
 m Ze2 8 0 n h n2
Note : 1. The significance of negative sign in the expression for energy is that (1) the
electron is bound to the nucleus and external energy is required to remove the electron
from the atom. (2) Also E is inversely proportional to n2. With increase in n, numerically
energy decreases but due of negative sign, E increases with increase in n and electrons in
outer orbits will have greater energy. (n = 1 is the ground state and n = 2,3,4 …are excited
states).
2. To calculate the radius of an electron orbit in case of H – atom, orbital velocity of the
electron and its energy the following constant values are used.
m = 9.1 x 10-31 kg, e = 1.6 x 10-19 C, 0 = 8.85 x 10-12 Fm-1, h = 6.63 x 10-34 Js, Z = 1.
The radius of the electron in the first Bohr orbit (n = 1 ) = 0.53Å.
The velocity of the first Bohr orbit (n = 1) is 𝜐 = 2.18 x 106 ms-1.
The energy of the electrons are E1 = -13.6eV (n = 1), E2 = - 3.4eV (n = 2),..….

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 Paper 601 - Unit 1 : Atomic Physics

Origin of spectral lines

Expression for the wave number of the emitted spectral line
A spectral line of an element results when an electron in the atom jumps from higher
energy level (outer orbit) to the lower energy level (inner orbit). If E 1 and E2 are the two
energy levels corresponding to inner orbit n1 and outer orbit n2 respectively, then from the
mZ 2 e 4  mZ 2 e 4 
Bohr’s postulate h = E2 – E1 or h = − −  − 2 2 2 
8 02 n22 h 2  8 0 n1 h 
𝑚𝑍 2 𝑒 4 1 1 c
or 𝜈 = [ − ]. If  is the wavelength of the emitted radiation, then  =
8𝜀02 ℎ3 𝑛12 𝑛22 
𝑐 𝑚𝑍 2 𝑒 4 1 1 1 𝑚𝑍 2 𝑒 4 1 1 1
= [ 2 − 2 ] or = [ − ] As = is called the wave number
𝜆 8𝜀02 ℎ3 𝑛1 𝑛2 𝜆 8𝜀02 𝑐 ℎ3 𝑛12 𝑛22 
𝑚𝑍 2 𝑒 4 1 1
of the emitted spectral line. It is given by 𝜈̅ = [ − ]
8𝜀02 𝑐 ℎ3 𝑛12 𝑛22
𝑚𝑒 4 1 1 1 1
For hydrogen atom Z = 1. Thus 𝜈̅ = [ − ] or 𝜈̅ = 𝑅𝐻 [𝑛2 − ]
8𝜀02 𝑐 ℎ3 𝑛12 𝑛22 1 𝑛22

m e4
where RH = is a constant called Rydberg constant (RH) for hydrogen atom (Here
8 02 ch3
the nucleus is assumed to have infinite mass and hence is at rest. Here m stands for mass
of the electron). The value of RH = Spectral series of H – atom
1.09678 x 107m-1. Transition Region of EM
Name of the
Bohr gave the explanation of spectral spectral series From n2 To n1
spectrum
series of hydrogen atom based on his Lyman 2,3,4,… 1 Ultraviolet
postulates as follows. Balmer 3,4,5,… 2 Visible
When energy is given to the electron Paschen 4,5,6,… 3 Infrared
Brackett 5,6,7,… 4 Farinfrared
in the ground state of an atom, it will
Pfund 6,7,8,… 5 ExtremeIR
rise to one of the permitted higher
energy states (outer orbits). As the electrons are unstable in these states, it will return to
ground state either in a single jump or a series of jumps. Each such transition of electron
from higher to lower energy state will result in the emission of electromagnetic radiation
of a particular wavelength. This corresponds to a line in the spectrum.
Note : A number of spectral lines in the hydrogen spectrum are observed even though
hydrogen atom has a single electron. The reason is the following
A hydrogen gas has a large number of atoms. If energy is supplied externally to a large
number of hydrogen atoms, all the electrons may not be excited to the same higher energy
state. Therefore different electrons undergo different transitions.

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 Paper 601 - Unit 1 : Atomic Physics
E=0 n=¥
Energy level diagram is a diagram
indicating the different energy states n=6

- 0.54eV n=5
corresponding to different values of quantum Pfund
series n=4
numbers (n) and the transitions of electrons
- 0.85eV
Brackett
series
between different energy states producing - 1.51eV n=3
Paschen
different spectral series. series

In the Energy level diagram, horizontal lines - 3.4eV n=2

Balmer
correspond to different energy values of the series

stationary states of the electrons. Vertical lines

are drawn to show the different transitions of
E
electrons between the orbits. The first
excitation energy is -3.4–(-13.6)= 12.09eV The
ionization energy of H – atom is 13.6eV. - 13.6eV n=1
Lyman
Bohr’s correspondence principle : For large series

values of n, the successive energy values differ very little. Thus the principle says – the
behavior of an atomic system as predicted by quantum theory tends asymptotically to that
expected in classical theory in transitions involving states of large quantum numbers.

Variation of Rydberg constant with nuclear mass

In Bohr’s theory, it was assumed that mass of nucleus is so heavy (nearly infinity) that it
remains at rest and the electron revolves round it in circular orbits. This is not true as the
mass of the nucleus is only 1836 times the mass of the electron. With a finite mass of the
nucleus, both the nucleus and the electron revolve about their common centre of mass
with the same angular frequency.
With this correction to Bohr’s theory, the mass of the electron, m is replaced by reduced
𝑚𝑀 𝑚
mass of the system given by 𝜇 = = 𝑚 where M is the mass of the nucleus.
𝑀+𝑚 1+
𝑀

The expression for Rydberg constant should be written as

𝜇𝑒 4 𝑚𝑒 4 1
𝑅=
8𝜀02 𝑐ℎ3
=
8𝜀02 𝑐ℎ3
( 𝑚 ) . This shows that Rydberg constant varies with mass of the
1+
𝑀

nucleus. If 𝑅∞ is the Rydberg constant when nucleus is at rest with its mass close to
infinity and 𝑅𝑀 is the Rydberg constant when nuclear mass is finite then
𝑅∞ 𝑚𝑒 4
𝑅 = 𝑅𝑀 = 𝑚 .Here 𝑅∞ = . The transition between two energy levels which
1+ 8𝜀02 𝑐ℎ3
𝑀

results in the emission of a spectral line of a particular wave number is given by

1 1 𝑅∞ 2 1 1
𝜈̅ = 𝑅𝑀 𝑍 2 [𝑛2 − ]= 𝑚𝑍 [ 2 − ].
1 𝑛22 1+ 𝑀 𝑛1 𝑛22

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 Paper 601 - Unit 1 : Atomic Physics

(a) The reduced mass 𝜇 < 𝑚. It increases with increasing nuclear mass M and becomes
equal to electronic mass as 𝑀 → ∞. For example in case of Hydrogen and Helium,
by considering the effect of finite mass of the nucleus, the values of 𝑅𝐻 and 𝑅𝐻𝑒 are
1.09677 × 107 𝑚−1 and 1.09722 × 107 𝑚−1. As 𝑅𝐻𝑒 > 𝑅𝐻 the spectral lines of
Pickering series of He+ should have slightly higher wave numbers or shorter
wavelengths than the corresponding lines of the Balmer series of hydrogen. These
values agree well with the experimental values giving justification for the motion of
the nucleus.
(b) Using the values of 𝑅𝐻𝑒 and 𝑅𝐻 , the ratio of mass of the electron to that of mass of
the proton i.e. 𝑚/𝑀𝐻 was found to be 1/1840 which is in excellent agreement with
the values obtained by other methods.
(c) The variation of R with M also resulted in the discovery of heavy hydrogen, called
deuterium whose nuclear mass is nearly double that of hydrogen nuclear mass.
The spectrum of the H atom were found to have faint lines on the shorter
wavelength sides of the spectral lines. This observation was attributed to the
presence of isotope of hydrogen called deuterium whose Rydberg constant was
found to be 𝑅𝐷 = 1.09707 × 107 𝑚−1 . The wave numbers calculated using this
agreed with the experimental values.

Limitations of Bohr’s theory

1. It applies only to one-electron atoms, particularly hydrogen atom.
2. As the electron revolves at a high speed, relativistic correction has to be applied to
its mass which is not considered in the Bohr’s theory.
3. The fine structure of the spectral lines could not be explained by Bohr’s theory.
4. When applied to hydrogen like atoms, (singly ionised helium, doubly ionised
lithium etc… which contain one electron around the nucleus like hydrogen) the
Bohr’s theory does not yield proper results.
5. The Bohr’s theory gives the frequency of the spectral lines but does not give any
information about their relative intensities.
6. Spectra of heavy elements and their chemical properties could not be explained
based on this theory.

Sommerfeld's modification of the Bohr atomic model

Spectral lines of the Balmer series of hydrogen spectrum actually consist of a number of
very fine lines. These lines were found when observed through an optical instrument of
high resolving power. These lines are called fine structure of the spectrum. They could

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 Paper 601 - Unit 1 : Atomic Physics

not be explained by Bohr’s theory. Sommerfeld modified Bohr’s theory. According to

Sommerfeld,
1. The path of electrons around the nucleus, in general is elliptical with the nucleus at
one of its foci. The circular orbit is only a special case of an elliptical orbit.
2. The velocity of the electron is very high and is different at different points of
elliptical path. This causes variation of mass of the electrons. Thus relativistic
variation of mass of the electron need to be considered. This results in splitting of
spectral lines giving rise to fine structure.
Y

Concept of elliptical orbits b

-e
r
Periodic motion under the inverse square law force
𝜙
leads to elliptic orbits. It was therefore postulated by
+Ze a X
Sommerfeld that, in an atom an electron moves in an
elliptic orbit with the nucleus located at a focus. In an
elliptic orbit, an electron can be located by two coordinates r (the radius vector) and 𝝓
(the azimuth angle) as shown. If 𝑝𝑟 and 𝑝𝜙 be the resolved components of the momentum
p of the electron along the radial direction and perpendicular to it, then according to
sommerfeld, the two quantum conditions are
∫ 𝑝𝑟 𝑑𝑟 = 𝑛𝑟 ℏ …(1)
and ∫ 𝑝𝜙 𝑑𝜙 = 𝑛𝜙 ℏ …(2)
where 𝑛𝑟 and 𝑛𝜙 are called the radial quantum number and azimuthal quantum number
respectively which take only positive integral values and are such that 𝑛 = 𝑛𝑟 + 𝑛𝜙
where n is the principal quantum number.
𝑛𝑟 ℎ 𝑛𝜙 ℎ
Here 𝑝𝑟 = and 𝑝𝜙 =
2𝜋 2𝜋
If 𝜀 is the eccentricity of the ellipse with semi major axis as a and semi minor axis as b, it
𝑛𝜙 𝑛𝜙
can be shown that 𝑛 = or √1 − 𝜀 2 = ….. (3)
√1− 𝜀 2 𝑛
𝑏
Also as 𝑏 = 𝑎√1 − 𝜀 2 , we have √1 − 𝜀 2 = ……(4)
𝑎
𝒃 𝒏𝝓
From (3) and (4) = ….(5) This condition determines the allowed elliptical
𝒂 𝒏
orbits. This relation indicates that when 𝑛𝜙 = 𝑛 , 𝑏 = 𝑎 , the orbit is circular. 𝑛𝜙 cannot
be zero because the ellipse degenerates to a straight line. Also 𝑛𝜙 cannot be greater than
𝑛 since in such a case 𝑏 > 𝑎 . Hence for a given value of n, 𝒏𝝓 can only assume 𝒏
different values. This means only 𝑛 elliptical orbits of different eccentricities are allowed.

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 Paper 601 - Unit 1 : Atomic Physics

For example n=4

n=4 𝑛𝜙 = 3 n=4
𝑛 = 4, 𝑤𝑒 ℎ𝑎𝑣𝑒 𝑛𝜙 = 1,2,3,4 𝑛𝜙 = 4 𝑛𝜙 = 2
n=4
𝑛𝜙 = 1
i.e. four possible orbits with three
elliptical of different eccentricities
and one circular for a = b.
It can be shown that with the introduction of elliptical orbits for electrons, the energy of
𝜇𝑍 2 𝑒 4
electron expression is 𝐸𝑛 = − . This expression does not depend on 𝑛𝜙 but only
8𝜀02 𝑛2 ℎ2

on n. Thus introduction of elliptic orbits does not give rise to new energy levels. Thus
Sommerfeld proposed the relativistic correction to explain the fine structure.

Relativistic correction to Sommerfeld’s elliptical orbits Since the velocity of an

electron in the innermost Bohr orbit is 0.007 times the velocity of light, the electron in the
𝑚0
elliptic orbit must undergo variation of mass according to the relation 𝑚 =
√1− 𝑣 2 /𝑐 2

where 𝑚0 is the rest mass and 𝑚 is the mass when electron moves with
velocity 𝑣 close to 𝑐.
The application of relativistic correction leads to the fact that there is a
slow precession of the plane of the major axis about an axis through its
one of the foci. This represents a Rosette curve as shown.
Applying the relativistic correction, the energy of the electron in a particular quantum
𝜇𝑍 2 𝑒 4 𝑍 2 𝛼2 𝑛 3
state represented by n and 𝑛𝜙 is found to be 𝐸𝑛 = − [1 + (𝑛 − 4)]
8𝜀02 𝑛2 ℎ2 𝑛2 𝜙

𝑒2 1
where 𝛼 is the fine structure constant given by 𝛼 = 2𝜖 𝑐ℎ = 137 .
0

The expression for 𝐸𝑛 is found to depend on both 𝑛𝜙 𝑎𝑛𝑑 𝑛 .Transitions corresponding to

various 𝑛𝜙 values is found to occur. Since the energy difference of these values are very
small, the frequency of the resulting spectral lines will be very close. Thus a group of
closely associated lines appear instead of a single line as explained in Bohr’s theory. The
selection rule for the transition is ∆𝑛𝜙 = ±1 which suggests a finite number of close
lines.

Fine structure of 𝑯𝜶 line : The transitions corresponding to the fine structure of 𝐻𝛼

line of Balmer series of Hydrogen atom are as shown. 𝐻𝛼 line results from the transition of
the electron from n = 3 to n = 2. For n = 3, there are three possible energy levels and for n
= 2, there are two possible energy levels. Six transitions are possible between them as

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 Paper 601 - Unit 1 : Atomic Physics

shown. But by selection

n =3
rule ∆𝑛𝜙 = ±1, only 𝑛𝜙 =
three transitions are 3 33
allowed. (continuous 2 32
1 31
vertical lines). The dotted
lines are forbidden. This
agrees with the
experimental results. n=2
Sommerfeld’s theory was
2 22
able to explain the fine
1 21
structure.

Failures of Sommerfeld theory : (1) It fails to predict the number of lines in the fine
structure. (2) It failed to give information regarding the relative intensities of the lines. (3)
It fails to explain the Zeeman effect and the Stark effect. (4) These theories could not be
applied to many electron systems. To explain these drawbacks Vector atom model was
proposed.

The Vector Atom Model

𝑝റ𝑙
The main contributors for this model are
Bohr, Sommerfeld, Uhlenbeck,
Goudsmith, Pauli, Stern and Gerlach.
The two main features of vector atom 𝑒
model are (1) spatial quantization and
(2) electron spin.

(1) Space quantization :

According to spatial quantization, the orientation of the electron orbits in space is
quantized. The plane of the orbit in space or the direction of orbital angular momentum
can take only certain selected orientations with respect to a preferred direction which
could be an external magnetic field (B). (𝐵 → 0),
The magnitude of orbital angular momentum of the electron is given by
ℎ
𝐿 = 𝑝𝑙 = 𝑙 = 𝑙ℏ where l is the orbital quantum number. The associated magnetic
2𝜋
moment is called the orbital magnetic moment 𝜇𝑙 . For a given value of principal quantum
number n, l can take n values from 0 to (n – 1). Thus for n = 3, l = 0, 1, 2. For a given value

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 Paper 601 - Unit 1 : Atomic Physics

of l, an orbit in space can have (2l + 1) orientations in space with respect to external
magnetic field. Then according to the space quantization rule, only those orientations of 𝑝⃗𝑙
are possible for which its components along the field direction can have values given by
ℎ
𝑝𝑙 𝑐𝑜𝑠𝜙 = 𝑚𝑙 = 𝑚𝑙 ℏ where 𝜙 is the angle between 𝑝𝑙 and the external field
2𝜋
direction in space, 𝑚𝑙 is the magnetic quantum number for orbital motion and can have
the possible values of 0, ±1, ±2, ±3, … … ± 𝑙 . i.e. 𝑚𝑙 can have (2l + 1) values.
For example, in case of 𝑙 = 2, 𝑚𝑙 = +2, +1, 0, −1, −2 .

(2) Spinning electron hypothesis: According to electron spin

hypothesis proposed by Uhlenbeck and Goudsmit, an electron in addition
to orbital motion has a spin motion. The spin motion is quantized. The
ℎ
magnitude of the spin angular momentum is 𝑝𝑠 = 𝑠 = 𝑠ℏ where s is
2𝜋
the spin quantum number. The value of 𝑠 = 1/2 . The associated
magnetic moment is called the spin magnetic moment 𝜇𝑠 . The spin angular
momentum has two orientations with respect to external magnetic field i.e. either parallel
or antiparallel to field.

Magnetic moment due to the orbital motion of the electron - Expression for
Bohr magneton
The orbital motion of the electron is equivalent to a current loop
which produces a magnetic field perpendicular to the plane of the
orbit. The magnetic field is characterized by a magnetic dipole
moment. The magnetic moment associated with the current loop is
𝜇𝑙 = 𝐼𝐴 .
𝑒
But the current is 𝐼 = and 𝐴 = 𝜋𝑟 2 where r is the radius
𝑇
of the electron orbit and T is the time period of revolution of the
electron.
𝑒
Thus the magnetic moment is 𝜇𝑙 = 𝜋𝑟 2
𝑇
2𝜋𝑟
If 𝜐 is the orbital velocity of the electron, then = 𝑇 . Substituting for T in the above
𝜐
𝜐 𝑒𝜐𝑟
equation, we get 𝜇𝑙 = 𝑒 𝜋𝑟 2 ( ) =
2𝜋𝑟 2
𝑒
If we multiply and divide the above equation by m, we get 𝜇𝑙 = (𝑚 𝜐 𝑟)
2𝑚

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 Paper 601 - Unit 1 : Atomic Physics
𝑒
or 𝜇𝑙 = 𝑝 where 𝑝𝑙 = 𝑚 𝜐 𝑟 called the orbital angular momentum of the
2𝑚 𝑙
𝑒 𝑒ℏ
electron. As 𝑝𝑙 = 𝑙ℏ, we get 𝜇𝑙 = 𝑙ℏ = ( ) 𝑙
2𝑚 2𝑚
𝒆ℏ
The magnetic moment is 𝝁𝒍 = ( ) 𝒍 = 𝝁𝑩 𝒍
𝟐𝒎
𝒆ℏ 𝒆𝒉 ℎ
Where 𝝁𝑩 = = . ( since ℏ = )
𝟐𝒎𝒆 𝟒𝝅𝒎𝒆 2𝜋

𝝁𝑩 is called the Bohr magneton. Its value is 9.273 × 10-24 JT-1.

𝜇𝑙 𝑒 𝑒
The ratio = 𝐺 is called the gyromagnetic ratio given by 𝐺 = or 𝐺 = 𝑔𝑙
𝑝𝑙 2𝑚 2𝑚

where 𝑔𝑙 is called the lande’s splitting factor and is equal to 1 for orbital motion of the
electron.
𝑒ℏ
Note : The electron also possess spin magnetic moment given by 𝜇𝑠 = ( ) 2𝑠
2𝑚
1 𝑒ℏ
As 𝑠 = , thus 𝜇𝑠 = ( )
2 2𝑚

Stern – Gerlach Experiment

In 1921 Otto Stern and W. Gerlach of Germany performed an experiment in which atomic
beams were deflected in a non-homogeneous magnetic field. The experiment provides a
direct proof of (i) existence of two spin states (±1/2 ) of the electron and (ii) the postulate
of space quantization.

Principle : According to the vector atom model, every atom is regarded as an elementary
magnet where the magnetic moment arises from the orbital and the spin motion of the
electron. If such an atomic magnet is placed in a non-homogeneous magnetic field, each
pole of the magnet experiences a different
force. This results in translational 𝑑𝐵
𝑝 (𝐵 + 𝑙 𝑐𝑜𝑠𝜃)
displacement of the atom when it moves in 𝑑𝑥
the magnetic field. Thus the atom deviates l b

from its straight line path. p𝐵 𝜃

a

Theory: Let 𝑙 be the length of an atomic

magnet (ab) with 𝑝 as its pole strength placed
𝑑𝐵
inclined at an angle 𝜃 in a non homogeneous 𝐵 𝐵+ 𝑙 𝑐𝑜𝑠𝜃
𝑑𝑥
magnetic field which changes along x axis as
𝑑𝐵 𝑑𝐵
. The forces on the two poles at a and b are p𝐵 and 𝑝 (𝐵 + 𝑙 𝑐𝑜𝑠𝜃) respectively.
𝑑𝑥 𝑑𝑥

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Couple acts on the magnet and a translatory force 𝐹𝑥 acts on the atomic magnet given by
𝑑𝐵 𝑑𝐵 𝑑𝐵
𝐹𝑥 = 𝑝 𝑙 𝑐𝑜𝑠𝜃 or 𝐹𝑥 = 𝑝 𝑙 𝑐𝑜𝑠𝜃 = 𝑀 𝑐𝑜𝑠𝜃 …..(1) where 𝑀 = 𝑝 × 𝑙
𝑑𝑥 𝑑𝑥 𝑑𝑥
called the atomic magnetic moment.
Let 𝑚 be the mass of the atom, 𝜐 its velocity of motion normal to the field, 𝐿 the length of
the path in the field and 𝑡 the time of flight.
𝐹𝑥 𝐿
The acceleration of the atom is 𝑎𝑥 = …..(2) and 𝑡 =
𝑚 𝜐
𝑀 𝑐𝑜𝑠𝜃 𝑑𝐵
Substituting for 𝐹𝑥 from (1) in (2), 𝑎𝑥 = ….(3)
𝑚 𝑑𝑥
The displacement 𝐷𝑥 of the atom along the field direction at the end of the time 𝑡 is given
1
by 𝐷𝑥 = 𝑎𝑥 𝑡 2 ….(4)
2
1 𝑀 𝑐𝑜𝑠𝜃 𝑑𝐵 𝐿 2
Substituting for 𝑎𝑥 from (3) and 𝑡 in (4) 𝐷𝑥 = (𝜐)
2 𝑚 𝑑𝑥
𝟏 𝝁 𝒅𝑩 𝑳 𝟐
or 𝑫𝒙 = (𝝊) where 𝜇 = 𝑀 𝑐𝑜𝑠𝜃 is the resolved magnetic moment in
𝟐 𝒎 𝒅𝒙
𝑑𝐵
the field direction. If 𝑚 , 𝐿, and 𝜐 are known, by measuring 𝐷𝑥 we can calculate 𝜇.
𝑑𝑥

Experimental description
P
S1 S2 Photographic
S plate
S

O
N
N
Shape of magnets
Furnace Beam of
Silver Slits non-homogeneous Without With
atoms magnetic field field field
Traces obtained
on the photo plate
O is the electric oven in which metallic silver is heated to produce a beam of silver atoms.
The velocity of the beam is controlled by temperature of the oven. The atomic rays
collimated by slits S1 and S2 will enter a non-homogeneous magnetic field produced by
magnets one with a sharp knife edge and other with a groove parallel to knife edge as
shown. P is the photographic plate. The complete apparatus is placed in an evacuated
chamber.
When the magnetic field is switched off, a sharp line was traced by the atomic beam on
the plate P. On switching on the field, a double trace was obtained on plate P as shown.
Since there are two possible values of 𝑚𝑠 (= ±1/2), the beam splits up into two. From the

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 Paper 601 - Unit 1 : Atomic Physics
𝑑𝐵
trace the deviation 𝐷𝑥 of the beam was measured accurately. Knowing 𝑚, 𝐿, and 𝜐
𝑑𝑥
the value of 𝜇 was calculated for silver. It was found to be equal to one Bohr magneton for
silver. This confirms the electron spin concept of the vector model.
Stren and Gerlach’s experiment also provides a direct proof of the idea of space
quantization. Since 𝐽 = 𝑗 = 1/2 in the present case, there are (2𝐽 + 1) or two possible
orientations of 𝐽 in the magnetic field. Hence the beam splits into two in the magnetic
field.

Quantum numbers associated with the vector model of the atom

In vector atom model, for each of the component parts like orbital and spin motion, orbital
and spin angular momentum, a quantum number is assigned. They are the set of integers
or half integers characterizing the energy states of an electron in an atom. Each electron in
an atom is described by four different quantum numbers. They are 𝑛, 𝑙, 𝑠 𝑎𝑛𝑑 𝐽. In a
strong magnetic field three more quantum numbers arise. They are 𝑚𝑙 , 𝑚𝑠 𝑎𝑛𝑑 𝑚𝐽 .

1. Principal Quantum Number (n): It specifies the energy of an electron and the size
of the orbital. It can take only integral values i.e. n = 1, 2, 3, ……,∞ . All orbitals
that have the same value of n are said to be in the same shell (level). 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 an excited state. The total number of orbitals for a given n value is n2.
2. Orbital Quantum Number (l): It specifies the shape of an orbital with a particular
principal quantum number. It takes integral values between 0 and 𝑛 − 1 i.e. l = 0, 1,
2, 3……, 𝑛 − 1. This quantum number divides the shells into smaller groups of
orbitals called subshells (sublevels). Usually, a letter code is used to identify l to
avoid confusion with n. For 𝑙 = 0,1,2,3,., the letters are s, p, d, f … respectively. The
ℎ
orbital angular momentum is quantized and is given by 𝑝𝑙 = 𝑙 2𝜋 = 𝑙ℏ. According

to wave mechanics 𝐿 = 𝑝𝑙 = √𝑙(𝑙 + 1) ℏ.

3. Spin Quantum number (𝒔) ∶ It is has a magnitude of ½. An electron can spin in
only one of two directions (sometimes called up or down). The spin angular
ℎ
momentum is quantized and is given by 𝑝𝑠 = 𝑠 2𝜋 = 𝑠ℏ. According to wave

mechanics 𝑝𝑠 = √𝑠(𝑠 + 1) ℏ.
4. Total angular Quantum number (𝒋) : It is the resultant of orbital and the spin
motion and is given by 𝑗 = 𝑙 + 𝑠 = 𝑙 ± 1/2. It is 𝑙 + 𝑠 when 𝑠 is parallel to 𝑙 and 𝑙 −
𝑠 when 𝑠 is antiparallel to 𝑙 .The total angular momentum is quantized and is given
ℎ
by 𝑝𝑗 = 𝑗 2𝜋 = 𝑗ℏ. According to wave mechanics 𝑝𝑗 = √𝑗(𝑗 + 1) ℏ.

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 Paper 601 - Unit 1 : Atomic Physics

5. Magnetic Quantum Number (𝒎𝒍 ) : It specifies

the orientation in space of an orbital of a given
energy (n) and shape (l). It is the projection of
the orbital vector 𝑙 on the external field
direction, i.e. Lz. It is an integer and can have
any of the (2𝑙 + 1) values from − 𝑙 𝑡𝑜 + 𝑙. This
quantum number divides the subshell into
individual orbitals which hold the electrons; there are 2𝑙 + 1 orbitals in each
subshell. Thus the s subshell has only one orbital, the p subshell has three orbitals,
and so on. If 𝑙 = 2, 𝑡ℎ𝑒𝑛 𝑚𝑙 = −2, −1, 0, +1, +2 as shown.
6. Magnetic Spin Quantum Number (𝒎𝒔 ) : It specifies the orientation of the spin
axis of an electron. It is the projection of the spin vector 𝑠 on the external field
direction. It can have 2𝑠 + 1 from – 𝑠 to + 𝑠
excluding zero. 𝑚𝑠 can have only two values
1 1
+ 2 𝑜𝑟 − 2. (Dia. 2)
7. Magnetic total angular momentum Quantum
number (𝒎𝒋 ) : It is the projection of the total
angular momentum vector 𝑗 on the external field
direction. It can have 2𝑗 + 1 from – 𝑗 to + 𝑗
excluding zero. (Dia 3)

Spectral terms and their notations

The different energy states of the atom between which transitions can take place are
referred in spectroscopic study as spectral terms. The fine structure is explained in terms
of spectral terms. In the classification of the spectral terms by the use of the vector atom
model, it is convenient to divide atoms into two main categories,

(a) One electron systems are those having only one valance or optical electron like
hydrogen atom and hydrogen like atoms such as alkali atoms. Even though in such atoms
there are several electrons, except one all other electrons are in closed shells which do not
contribute to the angular momentum of the atom. Only the valance electron contributes to
the spectral properties. The state of the atom is determined by this single free electron, the
values of 𝑙, 𝑠 𝑎𝑛𝑑 𝑗 referring to the electron are equal to 𝐿, 𝑆 𝑎𝑛𝑑 𝐽 defining to the whole
1
atom. Hence 𝑆 = 𝑠 = ± 2 and the multiplicity of the state is 𝑟 = (2𝑆 + 1) = 2. Thus the
system gives double terms with the exception of ground term which correspond to normal
state of the atom i.e. to 𝐿 = 0. Here the possible values of J are only two. i.e. 𝐽 = 𝐿 +

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 Paper 601 - Unit 1 : Atomic Physics
1 1 1
𝑎𝑛𝑑 𝐿 − . Now if 𝐿 = 0, 𝐽 = ± . The net angular momentum is always positive, the
2 2 2
1 1
only value of 𝐽 = + 2 which means a singlet. If 𝐿 = 1, 𝐽 = 1 ± 2 i.e. 3/2 and ½ (doublet).

(b) Many electron systems are those with more than one valance or many electrons
interlocked in closed shells which contribute to the total angular momentum and the
spectral properties Eg. Alkaline earths. As many free electrons determine the state of the
atom, the vectors 𝐿, 𝑆 𝑎𝑛𝑑 𝐽 defining the state of the atom will be the resultant of the
vectors 𝑙, 𝑠 𝑎𝑛𝑑 𝑗 of these electrons. Hence the value of 𝑆 is not always half, may be
1 3
0, 2 , 1, 2 , .. according to the number of electrons involved and their orientations i.e. parallel
or antiparallel. Also the multiplicity r is no longer 2 for all cases, but is 1 when 𝑆 = 0 and 2
1
when 𝑆 = 2 so on. Thus the possible values of 𝐽 for a given value of 𝐿 may be one, two,
three etc., which means each state may be a singlet or multiplet. For example in a two
electron system since 𝑆 = 0 𝑜𝑟 1, the state can be only a singlet or a triplet. In a three
1 3
electron system, as 𝑆 = 2 𝑜𝑟 2, each state can be a doublet or a quartet. In general odd
electron systems have even number of terms, while even electron systems have odd
number of terms.

Notations of spectral terms: The states of the system in which values of L vectors are
0, 1, 2, 3, 4, …. Are symbolically represented by the capital letters S, P, D, F, G,….
respectively. The value of 𝐽 is written as a subscript to this symbol and the multiplicity of
the state r written as a left superscript. For example the spectral terms corresponding to
1 2
𝐿 = 1 𝑎𝑛𝑑 𝑆 = 2 are written as 𝑃1 𝑎𝑛𝑑 2𝑃3 . This is because for L = 1, the letter is P and
2 2
1
multiplicity is 𝑟 = (2𝑆 + 1) = (2 × 2 + 1) = 2 which is the left superscript. Also as 𝐽 = 𝐿 ±
1 1 3
𝑆 = 1 ± 2 = 2 𝑜𝑟 2 which represent the subscripts.

Selection rules : They specify the possible transitions among quantum levels due to
absorption or emission of electromagnetic radiation. In vector atom model three selection
rules, one each for L, S and J have been devised.
The selection rule for L is given by ∆𝐿 = ±1 (not zero). i.e. only these lines are observed
for which the value of L changes by ±1 .
The selection rule for S is given by ∆𝑆 = 0. It means that states with different S do not
combine with each other. However both theoretical and experimental observations show
that this rule is not strictly adhered but is only approximate.

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 Paper 601 - Unit 1 : Atomic Physics

The selection rule for J is given by ∆𝐽 = ±1 𝑜𝑟 0 (0 → 0 𝑖𝑠 𝑒𝑥𝑐𝑙𝑢𝑑𝑒𝑑). i.e. spectral lines

arise only when transitions occur for which 𝐽 changes by ±1 .
Note : In the presence of a magnetic field, the orbital magnetic quantum number 𝑚𝑙 either
does not change or changes by ±1 i.e. ∆𝑚𝑙 = 0, ±1. Similarly ∆𝑚𝑠 = 0.

The intensity rules have been devised to supplement the selection rules, in order to
predict the intensity of lines that occur. They are
(a) The transitions are strong, giving intense lines in which L and J change in the same
sense and the transitions are weak when changes in L and J are different. For example
∆𝐿 = −1, ∆𝐽 = −1 (intense line) ∆𝐿 = −1, ∆𝐽 = 0 (less intense)
(b) Transition in the decreasing sense (𝐿 → 𝐿 − 1) is stronger than a transition in the
increasing sense (𝐿 → 𝐿 + 1) i.e. ∆𝐿 = +1, ∆𝐽 = +1 (weaker) ∆𝐿 = +1, ∆𝐽 = 0 (weakest).
(c) The case of oppositely directed transitions does not occur, in general and is forbidden
i.e. ∆𝐿 = −1, ∆𝐽 = +1 𝑜𝑟 ∆𝐿 = +1, ∆𝐽 = −1 (no line).

Coupling schemes
In atoms, with two or more electrons the orbital and spin angular momenta of all its
electrons can be added in two ways depending on the interaction or coupling between the
orbital and spin angular momenta. They are (a) the L –S
coupling and (b) the j – j coupling.

(a) L-S Coupling or Russell-Saunders Coupling: For

multi-electron atoms where the spin-orbit coupling is
weak, it can be presumed that the orbital angular momenta
of the individual electrons add to form a resultant orbital
angular momentum L. Likewise, the individual spin
angular momenta are presumed to couple to produce a
resultant spin angular momentum S. Then L and S
combine to form the total angular momentum.
𝑳 = 𝑳 𝟏 + 𝑳 𝟐 + 𝑳 𝟏 + ⋯ , 𝑺 = 𝑺𝟏 + 𝑺𝟐 + 𝑺𝟏 + ⋯ 𝒂𝒏𝒅 𝑱 = 𝑳 + 𝑺 .
This kind of combination is visualized in terms of a vector model of angular momentum.
When 𝐿 > 𝑆, 𝐽 can have (2𝑆 + 1). When 𝐿 < 𝑆, 𝐽 can have (2𝐿 + 1). This coupling
scheme is applicable in case of light atoms.

(b) j – j Coupling : For heavier elements with larger nuclear charge, the spin-orbit
interactions become as strong as the interactions between individual spins or orbital

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 Paper 601 - Unit 1 : Atomic Physics

angular momenta. In those cases the spin and orbital angular momenta of individual
electrons tend to couple to form individual electron angular momenta.
𝑱𝟏 = 𝑳𝟏 + 𝑺𝟏 , 𝑱𝟐 = 𝑳𝟐 + 𝑺𝟐 , 𝑱𝟑 = 𝑳𝟑 + 𝑺𝟑 … . 𝒂𝒏𝒅 𝑱 = 𝑱𝟏 + 𝑱𝟐 + ⋯

Pauli exclusion principle

The Pauli exclusion principle (Nobel Prize 1945) states that no two electrons in the same atom
can have identical values for all four of their quantum numbers. What this means is that no
more than two electrons can occupy the same orbital, and that two electrons in the same
orbital must have opposite spins. This is an example of a general principle which applies
not only to electrons but also to other particles of half-integer spin (fermions). It does not
apply to particles of integer spin (bosons).
In the modern view of atoms, the space surrounding the dense nucleus may be thought of
as consisting of orbitals, or regions, each of which comprises only two distinct states. The
Pauli exclusion principle indicates that, if one of these states is occupied by an electron of
spin one-half, the other may be occupied only by an electron of opposite spin, or spin
negative one-half.
The principle implies that each electron in an atom has a set of unique quantum numbers
𝑛, 𝑙, 𝑚𝑙 , 𝑎𝑛𝑑 𝑚𝑠 . Two electrons cannot have the same four quantum numbers. The
following table gives the distribution of electrons in various states.
Number of electrons in Total number
𝒏 𝒍 𝒎𝒍 𝒎𝒔 subshell with of electrons in
spectroscopic notation the shell = 𝟐𝒏𝟐
1 1
1 0 0 + ,− 2 1𝑠 2 2
2 2
2 0 0 1 1 2 2𝑠 2
+ ,−
2 2
8
1 1
2 1 −1, 0, +1 + ,− 6 2𝑝6
2 2
1 1
3 0 0 + ,− 2 3𝑠 2
2 2
1 1
3 1 −1, 0, +1 + ,− 6 3𝑝6 18
2 2
1 1
3 2 −2, −1, 0, +1, +2 + ,− 10 3𝑑10
2 2

Expression for maximum number of electrons in a shell

For a given sub shell, the values of 𝑛 𝑎𝑛𝑑 𝑙 are fixed. Only the values of 𝑚𝑙 and 𝑚𝑠 can
change. 𝑚𝑙 can take (2𝑙 + 1) values from – 𝑙 to + 𝑙. For each value of 𝑚𝑙 , 𝑚𝑠 can have

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 Paper 601 - Unit 1 : Atomic Physics
1 1
two values namely + , − . Thus the maximum number of electrons in any sub shell with
2 2
orbital 𝑙 is equal to 2(2𝑙 + 1).
Thus the total number of electrons with principal quantum number 𝑛 is equal to sum of
electrons in the constituent 𝑛 sub shells and is given by
𝑙= (𝑛−1) 𝑙= (𝑛−1)

∑ 2(2𝑙 + 1) = 2 ∑ (2𝑙 + 1)
𝑙=0 𝑙=0
= 2[1 + 3 + 5 + 7 + ⋯ {2(𝑛 − 1) + 1}]

= 2[1 + 3 + 5 + 7 + ⋯ (2𝑛 − 1)]

1
The quantity in bracket has n terms whose average value is 2 [1 + (2𝑛 − 1)]

Therefore the maximum number of electrons in a filled shell

𝑁𝑚𝑎𝑥 = 2(𝑛 𝑎𝑣𝑒𝑟𝑎𝑔𝑒 𝑣𝑎𝑙𝑢𝑒𝑠)

1
= 2(𝑛) [1 + (2𝑛 − 1)] = 𝑛[1 + (2𝑛 − 1)] = 𝑛 + 2𝑛2 − 𝑛
2
Thus 𝑵𝒎𝒂𝒙 = 𝟐𝒏𝟐

Thus a closed K – shell holds two electrons, a closed L – shell holds eight electrons, a
closed M – shell holds eighteen electrons and so on.

Spectra of alkali elements (Sodium D line)

The alkali elements like sodium, potassium, lithium etc. contain one valance electron in
the outermost shell and hence is hydrogen like. The spectra of these elements are similar
to that of hydrogen and are called alkali spectra. The frequency of a spectral line in the
1 1 1
alkali spectra is given by 𝜈̅ = = 𝑅 [(𝑛 − ]
𝜆 1 − 𝛼)2 (𝑛2 − 𝛽)2
where 𝛼 and 𝛽 are the characteristic constants of the given element and 𝑛1 = 1, 2, 3, … and
𝑛2 = 1, 2, 3, … Depending on the values of 𝑛1 and 𝑛2 we obtain the following series.
(1) When 𝑛1 = 1 and 𝑛2 = 1, 2, 3, 4, ….. we get the sharp series and its frequency is
1 1
given by 𝜈̅ = 𝑅 [ − ].
(1− 𝛼)2 (𝑛2 − 𝛽𝑠 )2
(2) When 𝑛1 = 2 and 𝑛2 = 2, 3, 4,5, . . ….. we get the principal series and its frequency is
1 1
given by 𝜈̅ = 𝑅 [ − 2 ].
(2− 𝛼)2 (𝑛2 − 𝛽𝑝 )
(3) When 𝑛1 = 3 and 𝑛2 = 3, 4,5, . . ….. we get the diffuse series and its frequency is
1 1
given by 𝜈̅ = 𝑅 [ − ].
(3− 𝛼)2 (𝑛2 − 𝛽𝑑 )2

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 Paper 601 - Unit 1 : Atomic Physics

(4) When 𝑛1 = 4 and 𝑛2 = 𝐿 𝐽

4,5, 6, . . ….. we get the 3 2
fundamental series and its 1 ⬚𝑃3
2 2
frequency is given by 𝜈̅ =
1 1 1 2
𝑅 [(4− 2 − ]. 1 ⬚𝑃1
𝛼) 2
(𝑛2 − 𝛽𝑓 ) 2 2

𝐷1 𝐷2
Fine structure of Sodium D line
The atomic number of sodium is 11.
Ten out of the 11 electrons are 1 2
0 ⬚𝑆1
interlocked in the closed shells. Only 2 2

the eleventh electron contributes to the

angular momentum of the atom resulting in the optical spectrum of the sodium atom.
The D-line belongs to the principal series. They are due to transitions from a P state to S
1 3
state. For the upper P state, 𝐿 = 1, 𝐽 = 𝐿 ± 𝑆 = 2 𝑜𝑟 2. Hence the two possible terms are
2
𝑃3 and 2𝑃1. For the lower S state, = 0, 𝐽 = 2 , so that only one term
1 2
𝑆1 is possible. The
2 2 2

diagram above shows the two possible transitions between the two terms of the P state
and the single term of the S state. They are (1) 2𝑃1 → 2𝑆1 which results in the D1 line
2 2
2 2
of wavelength 5896 Å and (2) 𝑃3 → 𝑆1 giving the D2 line of wavelength 5890 Å . Now
2 2

applying the selection rules ∆𝐿 = ±1 𝑎𝑛𝑑 ∆𝐽 = ±1 𝑜𝑟 0 (excluding 0 → 0), both the

transitions are allowed. This explains the doublet fine structure of the sodium D line.

Larmor precession :
Larmor theorem : The effect of a magnetic field on an electron
moving in an orbit is to superimpose on the orbital motion a
precessional motion of the entire orbit about the direction of the
𝐵𝑒
magnetic field with angular velocity 𝜔 given by 𝜔 = .
2𝑚
Explanation : Diagram 1 shows two positions of the vector 𝑙⃗ as it
precesses about the magnetic field at constant inclination and the corresponding positions
of the electronic orbit. Just as a mechanical top precesses in a gravitational field, an
electron in an orbit precesses in a magnetic field. This is called Larmor precession.

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Zeeman Effect
Zeeman effect is a magneto-optical phenomenon discovered by Zeeman in 1896. If a
source of light producing line spectrum is placed in a magnetic field, the spectral lines are
split into components. This phenomenon is called Zeeman effect. They are of two kinds,
(a) Normal Zeeman effect and (b) Anomalous Zeeman effect.

Experimental study of Zeeman effect.

The arrangement is as
shown in the diagram.
MM is a strong
electromagnet which
produces strong magnetic
field. Its conical pole
pieces PP have
longitudinal holes drilled
through them. A source of
light L (say sodium vapour lamp) producing line spectrum is placed between the pole
pieces. The spectral lines are observed with the help of a spectrograph S of high resolving
power. The Zeeman effect is observed in two ways.
(1) The spectral line is viewed without the application of magnetic field. Now the
magnetic field is applied and the spectral line is viewed longitudinally through the
hole drilled in the pole pieces and hence parallel to the direction of the magnetic
field. The spectral line is found to split into two components one with the longer
wavelength and the other with the shorter wavelength than the original line. The
original line is absent. These two lines are symmetrically situated on either side of
the original line. Analysing the two lines with the nicol prism , both are found to
be circularly polarized in opposite directions. This is called Normal longitudinal
Zeeman effect.
(2) When the spectral line is viewed along the transverse direction, i.e. perpendicular
to the magnetic field, it is found to split in to three components. The central line
has the same wavelength as that of the original line and is plane polarized with the
vibrations parallel to the direction of the field. The outer lines are symmetrically
positioned about the central line and both these lines are plane polarized with the
vibrations perpendicular to the magnetic field. The displacement of the either of
the two outer lines from the central line is called Zeeman shift. This is called
Normal transverse Zeeman effect.

VI Sem. B.Sc. Dr. K S Suresh Page 19

 Paper 601 - Unit 1 : Atomic Physics

Normal Zeeman Effect

The splitting of a spectral line into two or three components in a magnetic field is called
the Normal Zeeman effect. The experimental arrangement is explained above.

Quantum mechanical explanation of Normal Zeeman effect

Debye’s explanation of Normal Zeeman effect : Debye explained the Normal Zeeman
effect without taking into account the concept of electron spin. By
neglecting the spin motion, the orbital angular momentum of the
𝑙ℎ B
electron is 𝑝𝑙 = …..(1)
2𝜋
𝑒
The magnetic moment is given by 𝜇𝑙 = 𝑝 ……..(2)
2𝑚 𝑙
𝑝⃗𝑙
In the presence of an external magnetic field of flux density B, the 𝑝⃗𝑙
𝜃
vector l precesses around the direction of magnetic field as the axis.
This precession is the Larmor precession. The potential energy of the
electron due to interaction between orbital magnetic moment and the
magnetic field B is given by 𝑈𝑚 = −𝜇𝑙 . 𝐵
If 𝜃 is the angle between B and 𝑝𝑙 , then 𝜇𝑙 has a direction opposite to 𝑝𝑙 ,
thus 𝑈𝑚 = 𝜇𝑙 𝐵 𝑐𝑜𝑠𝜃 …(3)
𝐵𝑒
The frequency of the Larmor precession is 𝜔 = …..(4)
2𝑚
The diagram shows two positions of the vector 𝑝𝑙 as it precesses about the electronic orbit.
The effect of this precession is to change the energy of the system by an amount ∆𝐸 which
is the potential energy gained by the electron, given by ∆𝐸 = 𝜇𝑙 𝐵 𝑐𝑜𝑠𝜃 ….(5)
𝑒 𝑒 𝑙ℎ
Substituting (2) and (1) in (5) ∆𝐸 = 𝑝𝐵 𝑐𝑜𝑠𝜃 = 𝐵 𝑐𝑜𝑠𝜃
2𝑚 𝑙 2𝑚 2𝜋
𝐵𝑒 ℎ 𝐵𝑒
∆𝐸 = 𝑙 𝑐𝑜𝑠𝜃 . But = 𝜔 and 𝑙 𝑐𝑜𝑠𝜃 is the projection of 𝑙 on B = 𝑚𝑙 .
2𝑚 2𝜋 2𝑚
𝑒ℎ ℎ
Thus ∆𝐸 = 𝑚𝑙 𝐵 = 𝑚𝑙 𝜔 …..(6)
4𝜋𝑚 2𝜋
Now 𝑚𝑙 can have (2𝑙 + 1) values from +𝑙 to −𝑙 . Therefore, an external magnetic field
will split a single energy level into (2𝑙 + 1) levels. The d - state (l = 2) is split into 5
sublevels and the p – state (l = 1) is split in to 3 sublevels as shown.
Let 𝐸0′ be the energy of the level l = 1 in the absence of magnetic field and 𝐸𝐵′ be the
energy of this level in the presence of the field.
𝑒ℎ
Then 𝐸𝐵′ = 𝐸0′ + ∆𝐸 ′ = 𝐸0′ + 𝑚𝑙′ 𝐵 …(7)
4𝜋𝑚
Let 𝐸0′′ be the energy of the level l = 2 in the absence of magnetic field and 𝐸𝐵′′ be the
energy of this level in the presence of the field. Then

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 Paper 601 - Unit 1 : Atomic Physics
𝑒ℎ
𝐸𝐵′′ = 𝐸0′′ + ∆𝐸 ′′ = 𝐸0′′ + 𝑚𝑙′′ 𝐵 …(8)
4𝜋𝑚
The quantity of radiation emitted in the presence of magnetic field is
𝑒ℎ
𝐸𝐵′′ − 𝐸𝐵′ = (𝐸0′′ − 𝐸0′ ) + (𝑚𝑙′′ − 𝑚𝑙′ ) 𝐵
4𝜋𝑚
𝑒ℎ
or ℎ𝜈 = ℎ𝜈0 + Δ𝑚𝑙 𝐵
4𝜋𝑚
𝑒𝐵
or 𝜈 = 𝜈0 + Δ𝑚𝑙 …(9)
4𝜋𝑚
where 𝜈 is the frequency of radiation
emitted in the presence of magnetic field
and 𝜈0 is the frequency of emitted
radiation in the absence of field.
The selection rule for 𝑚𝑙 is
Δ𝑚𝑙 = 0 𝑜𝑟 ± 1. Hence we have three
possible lines.
They are
𝝂𝟏 = 𝝂𝟎 for 𝚫𝒎𝒍 = 𝟎 ….(10) 𝝂𝟏 = 𝝂𝟎 𝝂𝟑 𝝂𝟎 𝝂𝟐
𝒆𝑩
𝝂𝟐 = 𝝂𝟎 + for 𝚫𝒎𝒍 = +𝟏 ….(11)
𝟒𝝅𝒎
𝒆𝑩
𝝂𝟑 = 𝝂𝟎 − for 𝚫𝒎𝒍 = −𝟏 ……(12)
𝟒𝝅𝒎
The diagram above represents Normal Zeeman effect. Although there are nine possible
transitions, they are grouped into only three different frequency components as indicated
by equations (10), (11) and (12).
𝑒𝐵
The frequency shift is given by 𝑑𝜈 = ±
4𝜋𝑚
𝑐 𝑑𝜆 𝜆2
As 𝜈 = , 𝑑𝜈 = − 𝑐 or 𝑑𝜆 = − 𝑑𝜈
𝜆 𝜆2 𝑐
𝝀𝟐 𝒆𝑩
Thus the Zeeman shift in terms of wavelength is 𝚫𝝀 = 𝒅𝝀 = ± ( ) .
𝒄 𝟒𝝅𝒎

Anomalous Zeeman Effect

The splitting of a spectral line into more than three components in ordinary weak
magnetic field is called Anomalous Zeeman effect. The quantum mechanical analysis of
this effect is done by using spin of the electron along with orbital motion. Thus there are
two angular momentum vectors L and S associated with an electron. The total angular
momentum vector is
𝐽 =𝐿+𝑆 ….(1)
The magnetic moment due to orbital motion is

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 Paper 601 - Unit 1 : Atomic Physics
𝑒ℎ
𝜇𝑙 = 𝐿 (
4𝜋𝑚
) …. (2)
Similarly the magnetic moment due to spin motion is
𝑒ℎ
𝜇𝑠 = 2𝑆 (
4𝜋𝑚
) ….. (3)
𝜇𝑙 and 𝜇𝑠 are directed opposite to L and S respectively due
to negative charge of the electron.
The resultant magnetic moment 𝜇 is not along J, since L
and S precess around J, 𝜇𝑙 and 𝜇𝑠 must also precess about
J.
To find the resultant magnetic moment of the electron, each
of these vectors 𝜇𝑙 and 𝜇𝑠 is resolved into two components,
one along J and the other perpendicular to it. The value of the perpendicular component
of each vector, averaged over a period of the motion will be zero, since it is constantly
changing direction.
The effective magnetic moment of the electron will be 𝜇𝑗 = component of 𝜇𝑙 along J +
component of 𝜇𝑠 along J.
𝑒ℎ 𝑒ℎ 𝑒ℎ
𝜇𝑗 = 𝐿 cos(𝐿 . 𝐽) + 2𝑆 cos(𝑆 . 𝐽) = [𝐿 cos(𝐿 . 𝐽) + 2𝑆 cos(𝑆 . 𝐽) ]
4𝜋𝑚 4𝜋𝑚 4𝜋𝑚
𝐿2 + 𝐽2 − 𝑆 2 𝑆 2 + 𝐽2 − 𝐿2
But, according to cosine law, cos(𝐿 . 𝐽) = and cos(𝑆 . 𝐽) =
2𝐿𝐽 2𝑆𝐽
𝑒ℎ 𝐿2 + 𝐽2 − 𝑆 2 𝑆 2 + 𝐽2 − 𝐿2
Thus 𝜇𝑗 = [ + ] …..(4)
4𝜋𝑚 2𝐽 𝐽
𝑒ℎ 3𝐽2 + 𝑆 2 − 𝐿2 𝑒ℎ 𝐽2 + 𝑆 2 − 𝐿2
𝜇𝑗 = [ ] or 𝜇𝑗 = 𝐽[1+ ]
4𝜋𝑚 2𝐽 4𝜋𝑚 2𝐽2

Writing 𝐽2 = 𝐽(𝐽 + 1) , 𝐿2 = 𝐿(𝐿 + 1) and 𝑆 2 = 𝑆(𝑆 + 1)

𝑒ℎ 𝐽(𝐽+1)+ 𝑆(𝑆+1)− 𝐿(𝐿+1)
𝜇𝑗 = 𝐽[1+ ] ….. (5)
4𝜋𝑚 2𝐽(𝐽+1)
𝑱(𝑱+𝟏)+ 𝑺(𝑺+𝟏)− 𝑳(𝑳+𝟏)
The quantity 𝟏 + = 𝒈. ….(6) It is called Lande g factor. Its value
𝟐𝑱(𝑱+𝟏)

depends on L, S and J.
𝑒ℎ
Hence 𝜇𝑗 = 𝑔𝐽 …..(7)
4𝜋𝑚
If the atom is placed in a weak magnetic field, the total angular momentum vector J
precesses about the direction of the magnetic field as axis.
The change in energy or the additional energy ∆𝐸 due to the action of the magnetic field
𝑒ℎ
on the atomic magnet is ∆𝐸 = 𝜇𝑗 𝐵 𝑐𝑜𝑠(𝐽, 𝐵) = 𝑔𝐽 𝐵 𝑐𝑜𝑠(𝐽, 𝐵).
4𝜋𝑚
But 𝐽 𝑐𝑜𝑠(𝐽, 𝐵) = the projection of vector J on the direction of the magnetic field = 𝑚𝑗 .

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 Paper 601 - Unit 1 : Atomic Physics
𝒆𝒉
∆𝑬 = 𝑩𝒈 𝒎𝒋 …. (8)
𝟒𝝅𝒎
𝑒ℎ
The quantity 𝐵 is called a Lorentz unit. It is the unit of energy used for expressing the
4𝜋𝑚
splitting of the energy levels in a magnetic field.

Since 𝑚𝑗 has (2𝐽 + 1) values, a given energy let is split up into (2𝐽 + 1) sublevels with
application of the magnetic field. When this 𝑚𝑗 is subjected to the selection rule 𝑚𝑗 =
0 𝑜𝑟 ± 1, we get the transition shown in the above diagram for the sodium D-lines.
1 1
The ground state 2𝑆1/2 splits into two sublevels. Here, = 0, 𝑆 = 2 , 𝐽 = 2 , Hence g = 2.
1 1
Since 𝑚𝑗 can take + 2 and − 2 , 𝑔𝑚𝑗 can have the values +1 and −1. The following table
gives the values for the quantum numbers necessary for the determination of splitting
factor 𝑔𝑚𝑗 for each of the energy levels of the sodium D – lines.
2
The longest wavelength component 𝑃1/2 → 2𝑆1/2 splits into four lines. The shortest
wavelength component 2𝑃3/2 → 2𝑆1/2 splits into six lines.
State 𝑳 𝑺 𝑱 𝒈 𝒎𝒋 𝒎𝒋 𝒈
𝟐 1 1 1 1
𝑺𝟏/𝟐 0 2 , −2 1 , −1
2 2 2

𝟐 1 1 2 1 1 1 1
𝑷𝟏/𝟐 1 , −2 , −3
2 2 3 2 3
3 1 2
1 3 4 ,2 2,2
𝟐 2
𝑷𝟑/𝟐 1 1 3 2
2 2 3 −2 , −2 − 3 , −2

The introduction of electron spin has led to complete agreement between the experimental
results and the theory of Anomalous Zeeman effect.

VI Sem. B.Sc. Dr. K S Suresh Page 23