UNIT – III

ATOMIC MODELS AND SPECTRA

The atoms are the fundamental particles of an element having the same physical and chemical
properties. To explain the structure of atoms, atomic models are proposed.

Thomson’s Model

This is the irst model designed by [Link] in 1904. The model is also known as plum‑
pudding model or pumpkin model. According to this model an atom is spherical in shape. Neg‑
atively charged electrons are embedded in positively charged luid. Thus the atom is electrically
neutral.

Though Thomson’s model was a signi icant step in understanding a atomic structure it has sev‑
eral limitations.

• The model does not explain orbital motion of electrons in the atom.

• It fails to explain stability of atoms.

• The model does not explain the origin of atomic spectra.

• The model does not give the estimation of radius, size, excitation of atoms.
Rutherford’s Atomic Model

In Rutherford’s atomic model, the whole mass of the atom is assumed to be concentrated at the
center of the atom, known as ”nucleus”. The nucleus is positively charged. Around the nucleus,
the electrons are orbiting at different distances, similar to the way planets orbit around the Sun.
Hence, this model is known as the ”planetary model”. The force of attraction between the elec‑
trons and the nucleus makes electrons to orbit around the nucleus and makes the atom.

Limitations of Rutherford Model

• The Rutherford model does not explain stability of atoms.

• It fails to explain the origin of atomic spectra.

• The model does not explain the ine structure of the spectral lines.

Bohr’s Atomic Model

To overcome the drawbacks of Rutherford’s model, Niels Bohr proposed a new model to explain
the structure of hydrogen atom in 1913.

Bohr’s Postulate

1. The negatively charged electron orbit around the positively charged nucleus in a circular
orbit known as stationary orbit.

2. In a stationary orbit, the angular momentum of the electron of mass m orbiting with ve‑
locity v in a circular orbit of radius r is given by
 nh
mvr =
2π
where n is the principal quantum number n = 1,2,3,4,5,…

3. In stationary orbits, electrons does not emit radiation. An electron moves from a station‑
ary orbit of higher energy to another stationary orbit of lower energy by emitting radia‑
tion.

The frequency of the emitted radiation is,

E2 − E1
ν=
h

where E1 and E2 are the energies of the electron in stationary orbits and E2 > E1 .

The Limitations of Bohr’s Theory

Bohr’s theory is applicable only for hydrogen or hydrogen‑like atoms where one electron is or‑
biting around the nucleus. Bohr’s theory does not explain the ine structure of spectral lines,
splitting of spectral lines in magnetic ield and electric ield.

Bohr–Sommerfeld Model

In order to explain ine structure of spectral lines in atomic spectra, Sommerfeld developed a
new model called relativistic atom model or Bohr–Sommerfeld Model. According to this model,
the orbit of electron round the nucleus is elliptical. The circular orbit proposed by Bohr are
special cases of this model. Also, the velocity of electron varies in the orbit causing relativistic
variation of mass.

Limitations of Bohr Sommerfeld’s Model

1. This model could not explain spectra of alkali metals.

2. It could not explain variation of intensities of spectral lines.

3. It could not explain Zeeman effect or Stark effect.

Vector atom Model

Due to failure of different atomic models & theories, particularly in explaining atomic spectrum,
a new theory & model was brought up, which is called vector atom model.

The two main features of vector atom model are,

1. Space quantization.

2. Spinning electron hypothesis

Space Quantization

The discreteness of orientation of electron orbit is called space quantization. Due to orbital
motion of the electron there will be angular momentum (⃗l). The angular momentum of the re‑
volving electron will be in a direction perpendicular to the plane of the orbit & is given by the
Right Hand Thumb rule (If the encircled ingers give the direction of motion of the electron,the
direction of angular momentum is given by the thumb).

The magnetic moment is a vector quantity which is in the opposite direction to the angular mo‑
mentum.
⃗µl = iA

where
A = area enclosed by the orbit
i = current due to electron motion
According to vector atom model, the direction or orientation of electron orbits in space should
be quantized. To specify the direction of the electron orbit, we require a reference axis. This
reference axis is chosen along the direction of the applied magnetic ield.

Spinning Electron Hypothesis

According to Spinning Electron hypothesis, the electron spins about its own axis with its orbital
motion around the nucleus. According to quantum theory, the spin of the electron should also be
quantized. Thus, electrons have orbital angular momentum and orbital magnetic moment due
to their orbital motion. Similarly they have spin angular momentum & spin magnetic moment
due to spin motion. Then the total angular momentum should be the vector sum of orbital &
spin angular momentum. Similarly total magnetic moment will be the vector sum of orbital &
spin magnetic moment.

Quantum numbers associated with vector atom model

1. Principal quantum number (n):

The principal quantum number designates the energy shell or orbit starting form the in‑
nermost. It is represented by n. It takes the values as n = 1, 2, 3, ....

For the innermost ( irst) orbit n = 1, which is named as K shell

For 2nd orbit n = 2, which is named as L shell

For 3rd orbit n = 3, which is named as M shell

For 4th orbit n = 4,which is named as N shell

2. Orbital angular momentum quantum number ( l ):

This quantum number corresponds to sublevels or subshells. Commonly it is named as

orbital quantum number. This may take any integral value as 0, 1, 2, 3, ...., (n − 1), where n
is principal quantum number.

For example,

if n = 4 ; l = 0, 1, 2, 3

if n = 2 ; l = 0, 1
 An electron for which l = 0 is called s electron. Similarly an electron with l= 1 is called
p‑electron. l = 2 → d‑electron and so on. According to classical physics the orbital angular
momentum is given by,

Pl = l hˉ

l.h h
⇒ Pl = , sincehˉ =
2π 2π

According to wave mechanics, orbital angular momentum is given by,

√
Pl = l(l + 1) .ˉ
h
√ h
Pl = l(l + 1) .
2π

Then for S electron ( l = 0), Pl =0

h
√
Similarly for P electron ( l = 1), Pl = 2 2π
√ h
Similarly for d electron ( l = 2), Pl = 6 2π

Thus orbital angular momentum (Pl ) is quantized.

3. Spin angular momentum quantum number (s)

This quantum number corresponds to spin of the electron & has the value of magnitude
1
2
. By convention s = + 12 , if l is parallel to s and s = − 21 , if l is antiparallel to s. The spin
angular momentum according to classical physics is given by,

Ps = s hˉ

h
Ps = s
2π

According to wave mechanics,

√ h
Ps = s(s + 1) .
2π

4. Total angular momentum quantum number (j)

It represents the total angular momentum of the electron which is the sum of orbital &
spin angular momentum. i.e, j = l ± s (since spin can take two directions, clockwise or
anticlockwise).
 example:

let l = 2 , then j = l ± s ⇒ j = l + s or j = l − s

⇒j =2+ 1
2
= 5
2
or j = 2 − 1
2
= 3
2

Thus j can take only odd‑half integral values. The total angular momentum of the electron
is given by,

Pj = j hˉ = j · 2π
h
, according to classical physics
√ h
Pj = j(j + 1) 2π , according to wave mechanics

5. Magnetic orbital angular momentum quantum number (ml )

The projection of the orbital quantum number l on the magnetic ield (B) direction is
called magnetic orbital quantum number ml . ml is the component of l along the direction
of magnetic ield. i.e, ml = l cosθ, where θ = angle between l and B.

There are 2l + 1 possible values of ml . ml can take values from −l to +l, including zero.

If l = 2, ml = −2, −1, 0, 1, 2. For a given l, ml represents the permitted orientation of l

relative to B.

For an example: Let l = 3, then ml = −3, −2, −1, 0, 1, 2, 3

 Thus for l = 3 the electron orbit can be oriented in seven different modes relative to B. l can
not be inclined at any other angle. Thus the orientation of electron orbit along permitted
direction in an atom is called spatial quantization.

6. Magnetic spin angular momentum quantum number (ms)

The projection of spin quantum number along the direction of applied magnetic ield is
called magnetic spin quantum number, (ms). This quantum number can assume only two
values, + 12 and − 12 . The relation connecting magnetic spin quantum number and spin
quantum number is given by
ms = S cos θ

where θ is the angle between S and B.

7. Magnetic total angular momentum quantum number(mj)

Magnetic total angular momentum quantum number is the projection of total angular mo‑
mentum quantum number j on the ield direction and it is given by

mj = j cosθ

where θ is the angle between j&B. For given value of j, there will be 2j + 1 values of mj
excluding zero.

For example: let j = 3/2 then mj = − 32 , − 12 , + 12 , + 23 .

Coupling Schemes

The process of adding orbital and spin angular momentum in an atom is called coupling. There
are two types of coupling. They are L‑S coupling (Russel‑Sander’s) & j − j coupling.

• L‑S Coupling: In this type of coupling all the orbital angular momentum vectors of various
electron combined to form a resultant L. Similarly all the spin angular
momentum vectors are combined to form a resultant S. The L‑S coupling can be
represented as,
(l1 + l2 + l3 + l4 + . . .) ⇒ L

(s1 + s2 + s3 + s4 + . . .) ⇒ S

L+S =J
 • j‑j Coupling:

The orbital and spin angular momentum of each electron are added to obtain total angular
momentum j of the electron. Then the total angular momentum of each electron will be
added to get the resultant as the total angular momentum of the entire atom as J.

The j‑j coupling is represented as,

l 1 + s 1 = j1

l 2 + s 2 = j2

l 3 + s 3 = j3 and so on.

j 1 + j2 + j 3 + . . . = J

Spectral notation:

A given energy state of an atom will be represented by a spectroscopic notation. For the single
electron system, the spectroscopic notation is of the form,

nlj 2S+1

where n is the principal quantum number, l is orbital angular momentum quantum number, j is
total angular momentum quantum number, 2S + 1 is the multiplicity with S as the spin of the
electron ( 21 ).

For example, an energy state with n = 2, l = 1, s = 1

2
and j = 3
2
is represented as 2P 3 2 . Here
2

l = 1 corresponds to p‑electron. ∴ l = 1 is represented by P in the notation. Similarly if an

energy state is represented as,
3S 1 2
2

1 1
will have n = 3, l = 0, j = 2
& s = 2
. But generally the spectroscopic nota‑
tion of an energy state is represented as nlj, by hiding multiplicity. That means a notation
3S 1 2 is practically written as 3S 1 .
2 2

Example:

1. write spectroscopic notation and draw energy level diagram for an atom n = 2, l = 1 &
s = 12 .

Soln: We have ,
j =l±s
⇒j =l+s and j =l−s
j =1+ 1
2
and j =1− 1
2

∴ j= 3
2
and 1
2

Multiplicity = 2S + 1
= 2 × 21 + 1
= 2

Therefore there are 2 energy states. The spectral notations of two states are 2P 3 and 2P 1 .
2 2

The energy states are as shown below,

2. Show that S‑state (Ground state) is always a singlet.

Soln:
1
Let n = 1, l = 0 & s = 2

1 1
Then j = l + s = 0 + 2
= 2

&j =l−s=0− 1
2
= − 12

But the −ve value for j (total angular momentum) is not possible and hence this case is
forbidden. Therefore there will be only one energy state for l = 0, that means S‑state is a
singlet. The energy orbit with spectral notation is as shown below.
Selection rules

The transition of electrons between energy states will obey certain rules which are called selec‑
tion rules. That means transition of electrons between different energy states may not occur in
random manner. There are three selection rules in vector atom model.

• Selection rule for l:

During transition there will be change in orbital angular momentum quantum number
and change should be ∆l = ±1, whereas ∆l = 0 is not allowed (forbidden). (∆l = +1 for
emission and ∆l = −1 for absorption line). As an example, transition between S and P
level is allowed (∆l = ±1) whereas between S and D (∆l = ±2) is not allowed. Moreover
transition between two S level, P, D, F levels is also not allowed.

• Selection rule for j:

The electron transition may occur between any two levels if ∆j = ±1 or 0.

• Selection rule for s:

The selection rule for s is given by

∆S = 0.

Pauli’s exclusion Principle:

Statement:

No two electrons in an atom can have same set of quantum numbers. This principle implies that
each electron in an atom must have a different set of quantum numbers n, l, ml and ms .

Applications:

Consider K shell with n = 1, l = 0, ml = 0, ms = + 12 & − 12 . Thus K shell can have two electrons,
one with quantum numbers n = 1, l = 0, ml = 0, ms = + 12 and the other with n = 1, l = 0, ml =
0, ms = − 12 . If there was a third electron, its quantum number would be identical with that of
the irst or second electron which is against Pauli’s exclusion principle. Thus the K shell can
have only two electrons.

• For L‑shell n = 2, l = 0 & 1.

• For the subshell n = 2, l = 0; ml = 0, ms = + 12 & − 12 . Hence there will be only two

electrons in this subshell.

• For the subshell n = 2, l = 1; ml can have 3 values i.e., −1, 0, 1.

• For each of these three values of ml , ms will be + 1

2
& − 12 .

Hence there will be six possible set of values for the quantum numbers.
Therefore there will be a maximum of six electrons in this subshell. Thus L shell with two
subshells will be full when it contains 2 + 6 = 8 electrons. For M shell with n = 3 there can
be three subshells with l = 0, 1, 2. The irst and second subshells are completed by two and
six electrons as explained above. The third subshell (l = 2) and (ml = −2, −1, 0, 1, 2) will
require 10 electrons to ill completely. Thus, M shell will be completely illed with 18 electrons.
Similarly N‑shell can have a maximum of 32 electrons.

Thus we come to the following conclusions:

a) In the nth shell there are n subshells corresponding to the values l = 0, 1, 2, 3, . . . , (n − 1).
The maximum number of electrons in a subshell with a given value of l is 2(2l + 1).

b) The number of electrons that can be accommodated in a shell with principal quantum
number n = The sum of the electrons in the constituent subshells.

∑n−1
The total number of electrons in a shell = l=0 2(2l + 1)
∑n−1
= 2 l=0 (2l + 1) = 2[1 + 3 + 5 + . . . + 2(n − 1) + 1]
= 2n2 [ ∵ 1 + 3 + 5 + . . . + 2(n − 1) + 1 = n2 ]
Fine Structure of Sodium‑D (Na‑D) Lines

The atomic number of sodium is 11. Its electronic con iguration is 1s2 2s2 2p6 3s1 . In the spec‑
trum of sodium atom two closely lying lines with wavelength 5896Ao and 5890Ao are observed.
As it is clear from the electronic con iguration, the outermost shell (n = 3) of sodium has one
electron. This electron is responsible for the observed closely lying lines ( ine structure) in the
spectrum. The energy level diagram of sodium for n = 3 state is as shown above.

In the normal state the electron will be in the 3s state. When external energy is supplied it will
be excited to the 3p state. When the excited electron returns back to the 3s state, D1 and D2 lines
will be emitted as shown in the diagram.

Magnetic Moment of an Atom due to Orbital Motion of Electron (µl )

Consider an electron orbiting around the nucleus of an atom in an elliptical orbit with r as the
radius vector. Since the electron is a charged particle, it produces a current. i.e,

e
i=
T
where e is the charge of the electron and T is the time period.
Since current produces a magnetic ield, the atom behaves as a tiny magnet or magnetic dipole.
The intensity or strength of the magnetic ield is measured by the magnetic moment. The mag‑
netic moment is given by cappler’s law,

µl = iA

where A is the area enclosed by the orbit. Then we have

(e)
µl = A . . . (1)
T
The areal velocity (rate at which the radius vector covers the area) is given by

dA 1
= r2 θ̇
dt 2
where θ̇ is the angular velocity. Then we have,

1
dA = r2 θ̇ dt
2

∫ T
1 2
A= r θ̇ dt
0 2

∫ T
1
A = r2 θ̇ dt
2 0

1
A = r2 θ̇ T
2
Substituting A in Eq. (1),

( e ) (1 )
2
µl = r θ̇T
T 2
( )
er2 θ̇
µl = . . . (2)
2

The angular momentum of an electron in orbital motion is given by

L = mvr

= m(rω)r (∵ v = rw)

= mr2 ω
 L = mr2 θ̇ (∵ θ̇ = w)

L
⇒ r2 θ̇ =
m
Substituting into the equation (2),

eL
µl = . . . (3)
2m
We have

√ h
L = Pl = l(l + 1) (known result)
2π
Then
e √ h
µl = l(l + 1)
2m 2π
eh √
= l(l + 1)
4πm
√
= µB l(l + 1)
eh
where µB = 4πm
is called the Bohr magneton.
µB = 9.274 × 10−24 JT−1
The signi icance of Bohr magneton is that it shows that magnetic moment is quantized.

Gyromagnetic ratio

It is the ratio of magnetic moment (µl ) to angular momentum (L).

µl
i.e., Gyromagnetic ratio = L

From (3), we have,

µl e
=
L 2m
= 8.8 × 109 C kg−1

Magnetic Moment Due to Spin Motion of an Electron

The expression for the magnetic moment due to spin is given by

√
µs = 2µB s(s + 1)

where
 • µB is the Bohr magneton.

• s is the spin quantum number.

Total Magnetic Moment of an Atom

The expression for the total magnetic moment is given by

√
µj = g. µB j(j + 1)

where

j(j + 1) + s(s + 1) − l(l + 1)

g =1+
2j(j + 1)
called the Landeś g‑factor.

Additional energy gained due to external magnetic ield in an atom

When an atom is placed in a magnetic ield of lux density B, the magnetic moment due to or‑
bital motion precesses around the direction of the magnetic ield. This phenomenon is called
Larmour precession. The frequency with which the orbital magnetic moment µl precesses
around magnetic ield is called the Larmour frequency.
The additional energy gained by the atom is given by

∆E = µ⃗l · B
⃗

= µl B cos θ (where θ is the angle between µl and B)

√ ( √ )
= µB l(l + 1) .B cos θ ∵ µl = µB l(l + 1)
( √ )
= µB .l B cos θ ∵ l(l + 1) ≈ l

= µB .B .l cos θ

⇒ ∆E = µB Bml
( )
eh
= Bml (∵ ml = lcosθ)
4πm

Zeeman Effect

Splitting of spectral lines into components in a magnetic ield is called the Zeeman effect.

• Splitting of a spectral line into two or three components in a strong magnetic ield is called
the normal Zeeman effect.

• Splitting of a spectral line into more than three components in a weak magnetic ield is
called the anomalous Zeeman effect.

Experimental Arrangement for Observing Normal Zeeman Effect

As shown in the diagram, H–H is a strong magnetic ield with pole pieces M –M . A source of
line spectrum L is placed between the pole pieces as shown. The spectral lines are observed
through powerful spectrographs (used to photograph or record spectra). In the absence of an
applied magnetic ield, the original single spectral line is observed at its normal position.

If the magnetic ield is switched on and the spectral line is viewed longitudinally through the
hole drilled in the pole pieces, the spectral line is observed to split into two components, one
having a higher frequency and the other a lower frequency than the original line. The original
line is absent in the observed spectrum. The two components are symmetrically situated about
the position of the original line. This is called the Normal Zeeman Effect ‑ Longitudinal View.

If the spectral line is viewed transversely (vertically), i.e., in a direction perpendicular to the
magnetic ield, the spectral line is found to split into three components. The central line has the
same frequency (or wavelength) as the original line, while the other two lines are symmetrically
situated on either side of the central line, one with a lower frequency and the other with a higher
frequency than the original line. The displacement of either outer line from the central line is
called the Zeeman Shift (dν or dλ).

Quantum Mechanical Theory of Zeeman Effect

In the normal Zeeman effect, a strong magnetic ield is considered and the spin of the electron is
neglected. The additional energy gained by an atom in the presence of a magnetic ield is given
by

eh
∆E = .[Link]
4πm
For a given value of l, ml can take (2l + 1) values in the applied magnetic ield B. This means
that the effect of the magnetic ield is to split each energy level of a given l into (2l + 1) levels.
Thus, the splitting of a spectral line into a number of components in the presence of a magnetic
ield (Zeeman effect) provides experimental proof of the space quantization or the vector atom
model.

• Let E ′ and EB′ be the energy levels in the absence and presence of a magnetic ield, respec‑
tively, for a given value of l.

• Let E ′′ and EB′′ be the energy levels in the absence and presence of a magnetic ield, re‑
spectively, for another value of l.

Then we have
EB′ = E ′ + ∆E ′ (1)

EB′′ = E ′′ + ∆E ′′ (2)

where ∆E ′ and ∆E ′′ are the additional energies gained in each case. When the transition be‑
tween these two energy levels occurs, the energy radiated is given by

EB′′ − EB′ = (E ′′ − E ′ ) + (∆E ′′ − ∆E ′ ) From Eqs. (1) and (2)

( ) ( )
eh eh
hν = hν0 + B m′′l − B m′l
4πm 4πm
Dividing throughout by h,
)(
eB
ν = ν0 + (m′′l − m′l )
( 4πm )
eB
⇒ ν = ν0 + ∆ml ...(3)
4πm
where, ∆ml = m′′l − m′l

The selection rule for ml is given by, ∆ml = 0, ±1

If ∆ml = 0 From Eq. (3),

ν = ν0 (original line)

If ∆ml = +1

eB
ν = ν0 + (higher frequency)
4πm
 If ∆ml = −1

eB
ν = ν0 − (lower frequency)
4πm
The spectral line with frequency ν = ν0 is called the parental or original line. The line with
eB
frequency ν = ν0 + 4πm
has a higher frequency than the original line. The spectral line with
frequency ν = ν0 − eB
4πm
has a lower frequency than the original line. The Zeeman shift is given
by,
∆ν = ν ∼ ν0
eB
=
4πm)
(
e 4π
⇒ = ∆ν
m B
where e/m is called the speci ic charge of an electron.
The Zeeman shift can also be expressed in terms of wavelength λ. We have,

c
ν=
λ
Differentiating with respect to λ,

∆ν c
= − 2
∆λ λ
∆ν c
= (neglecting the negative sign)
∆λ λ2
(c)
∆ν = ∆λ
λ2
( 2)
λ
∆λ = ∆ν
c
( 2)( ) ( )
λ eB eB
= ∵ ∆ν =
c 4πm 4πm

Normal Zeeman effect occurs only in atoms with an even number of electrons, since the spins of
the electrons cancel each other leading to neglect of spin.

Anomalous Zeeman Effect

Anomalous Zeeman effect occurs in atoms where both orbital and spin motions contribute to
the magnetic moment. Hence, the total angular momentum quantum number j and the associ‑
ated energy levels must be considered. For each value of j (total angular momentum quantum
number), there will be 2j + 1 values of mj (magnetic total angular momentum quantum number),
including zero. Thus, there will be more possible transitions between energy levels compared
to the normal Zeeman effect.
Hence, the number of component lines in the anomalous Zeeman effect is greater than that
in the normal Zeeman effect.

Spin–Orbit Interaction

An electron revolving around the nucleus experiences a force due to the magnetic ield asso‑
ciated with the nucleus. The splitting of spectral lines can be produced due to the interaction
of the electron with the magnetic moment of the nucleus. This interaction is called spin–orbit
interaction.

Additional energy gained in an external magnetic ield in terms of total an‑

gular momentum

Suppose an atom is placed in a magnetic ield of lux density B. Then the additional energy
gained by the atom,

∆E = µ⃗j · B
⃗

= µj B cos θ (where θ is the angle between µj and B)

Here, µj is the total magnetic moment.

√ ( √ )
∆E = gµB j(j + 1) .B cos θ ∵ µj = gµB j(j + 1) g − landersf actor
( √ )
= gµB .jB cos θ ∵ j(j + 1) ≃ j

= gµB .B(j cos θ)

∆E = gµB Bmj (∵ j cos θ = mj )

Stern–Gerlach Experiment

This experiment provides experimental proof for the spin of electrons and the concept of space
quantization. The experimental setup for performing the Stern–Gerlach experiment is shown
below.
The electric oven produces silver atoms. The beam of atoms is focused through the slits S1 and
S2 and then passed between two magnetic pole pieces N and S, which produce a non‑uniform
(non‑homogeneous) magnetic ield. The magnetic pole pieces are designed such that one of
them is in the shape of a knife edge which runs over the channel of the other, as shown in the
igure.

In the absence of a magnetic ield, there is a single beam of silver atoms which falls on the photo‑
graphic plate. However, in the presence of a magnetic ield, the beam splits into two and forms
two lines on the photographic plate. The silver atom contains 47 electrons, with a single elec‑
tron in the outermost orbit. This electron is in the S‑state. The S‑state is a singlet state (l = 0).
Then, for this S‑electron,
1
j=+
2
For a given value of j, there are (2j + 1) possible values of mj when a magnetic ield is applied.
( )
Thus, for silver atoms there will 2 21 + 1 = 2 values of mj are possible. The two values of mj
are mj = + 12 and mj = − 12 Thus, a single beam with a single value of j (j = 21 ) there will be two
1 1
beams produced in the presence of a magnetic ield. (∵ mj = + & − ).
2 2
Theory of Stern–Gerlach Experiment

The energy gained by silver atoms as they pass through the magnetic ield is given by

∆E = gµB Bmj

where

• g = Lander’s g‑factor

• µB = Bohr magneton

• B = magnetic ield

• mj = magnetic total angular momentum quantum number

For s‑electrons in silver atoms, g = 2 and mj = ± 12 Therefore,

( )
∆E = 2µB B ± 12

= ±µB B

The force experienced by each atom is given by

 d(∆E) ( )
Fy = work, W = F.S ⇒ F = W
S
⇒F = E
S
∵W =E
dy
d
= (±µB B)
dy
dB
⇒ Fy = ±µB . . . (1)
dy
dB
where is the ield gradient.
dy

The atomic beam passes through the narrow channel between the pole pieces and comes out of
the ield. Let δy be the vertical displacement when the beam comes out of the ield.
Then,

( )
δy = 1
a t2
2 y
. . . (2) ∵ s = ut + 12 at2 If u = 0, s = 12 at2

where ay is the acceleration and t is the time.

Let V be the velocity of the beam when it passes through a channel of length L.
Then,
L
t =
V
Fy = may
Fy
⇒ ay =
m
Substituting the values of t and ay in equation (2) ,

( )( )
1 Fy L 2
δy = 2 m V
( ) ( )
L2
⇒ δy = ± 12 µB dB
dy
1
m V2
. . . (3)

From electromagnetic theory, 12 mV 2 = 32 kT , where k is the Boltzmann constant.

Therefore,

mV 2 = 3kT

Substituting this value in equation (3),

( )( )
L2
δy = ± 12 µB dB
dy 3kT

Hence,

( )( )
µB L 2
δy = ± 6kT
dB
dy
Reference:

1. Murugeshan, R. & Sivaprasasth, K. (2014). Modern Physics. S. Chand & Company, New
Delhi, India.

2. Arthur Beiser, (6th Edn.) Concepts of Modern Physics., McGraw Hill Publishers.

3. Rajkumar (2022) . Atomic & Molecular Spectra: Laser. Kedarnath Ramanath, Meerut, U. P.

4. Murugeshan, R. (1992). Modern Physics. S. Chand & Company, New Delhi, India.
 QUESTION BANK

1 Mark Questions:

1. Who introduced the concepts of elliptical orbits for electrons in an atom?

2. Write expression for the total angular momentum of an electron in an atom according to
the wave‑mechanical model.

3. If j = 52 , what are the possible values of mj for an electron?

4. What is the maximum value of electrons that can be accommodated in a given orbit with
the principal quantum number n?

5. What is space quantization?

6. If an energy state of electron in an atom is represented as, nlj 2s+1 , what does j stands for?

7. State Pauli’s exclusion principle.

8. Write the expression for Bohr’s magneton.

9. Into how many distinct components does the sodium D‑line split?

10. What is gyromagnetic ratio?

11. What is Larmour precession?

12. What is Larmour frequency?

13. What is the normal Zeeman effect?

14. What is the anomalous Zeeman effect?

15. What is Zeeman shift?

16. What is Zeeman effect?

17. Which experiment provided proof for the concepts of electron spin and space quantiza‑
tion?

18. What type of magnetic ield is used to split the atomic beam in the Stern–Gerlach
experiment?

19. What should be the net spin of the system in order to observe the normal Zeeman effect?
 2 Mark Questions:

1. Give two limitations of Rutherford’s/Bohr’s model.

2. What are the allowed values of magnetic orbital quantum number for given value of orbital
quantum number?

3. Explain j − j coupling.

4. Explain L‑S coupling.

5. Why is S‑level always singlet?

6. Distinguish between normal and anomalous Zeeman effect.

7. Give the ine structure of Na‑D line of sodium.

8. De ine gyromagnetic ratio and write its value for an electron.

9. Write expression for Zeeman shift and explain the terms.

10. Write an expression for speci ic charge of an electron and explain the terms.

11. Give Two limitations of Bohr‑Sommerfeld model.

12. What is the signi icance of orbital quantum number l?

4 Mark Questions:

1. Explain L‑S coupling and j − j coupling in an atom.

2. State and explain Pauli’s Exclusion Principle.

3. Obtain an expression for magnetic moment of an electron due to its orbital motion in an
atom.

4. With a neat labeled diagram, explain experimental arrangement required to observe nor‑
mal Zeeman effect.

5. Explain quantum mechanical theory of Zeeman effect.

6. With required diagram, explain experimental arrangement in Stern–Gerlach experiment.

7. Obtain an expression for vertical displacement of atomic beam in Stern–Gerlach

experiment.
7 Mark Questions:

1. Explain various quantum numbers associated with vector atom model.

2. Describe experimental arrangement to observe normal Zeeman effect and explain its
quantum mechanical theory.

3. Describe the experimental arrangement and discuss the theories of Stern–Gerlach exper‑
iment.

4. Obtain expression for magnetic moment of an electron due to the orbital motion. Hence
obtain the expression for total magnetic moment.

5. Explain the quantum mechanical theory of normal Zeeman effect. Explain Zeeman shift
and hence obtain the expression for speci ic charge of an electron.
Numerical Problems:

1. Write spectroscopic notation and draw energy level diagram for an atom with n = 3.

2. The value of Bohr magneton is 9.2 × 10−24 J T−1 and Plank’s constant is 6.62 × 10−34 J s.
Calculate speci ic charge of electron. (Ans : 1.743 × 10−11 [Link] −1 )

3. The most prominent calcium line has wavelength 450 nm. Calcium atom exhibits normal
Zeeman effect in a magnetic ield of 5 T. Calculate wavelength of component lines and
separation between them. ( me = 1.758 × 1011 C Kg−1 , c = 3 × 108 ms−1 )
(Ans : 450.047 nm, 449.953 nm, 94.47 × 10−12 m)

4. Spectral line of 589 nm in a magnetic ield of 25 T becomes triplets under normal Zee‑
man effect. Calculate Zeeman shift and wavelength of component lines. ( me = 1.758 ×
1011 C Kg−1 ) (Ans : ∆λ = 4.04 × 10−10 m, 589.40 nm, 588.59 nm)

5. A spectral line of frequency 1014 Hz became triplet under normal Zeeman effect. Calcu‑
late Zeeman shift and frequencies of component lines. Also ind the separation between
component lines. (B = 50 T, e = 1.6 × 10−19 C, m = 9.1 × 10−31 Kg)

(Ans : 6.99 × 1011 Hz, 10.006 × 1014 Hz, 9.993 × 1011 Hz).

6. A beam of silver atoms in Stern–Gerlach experiment obtained from an oven heated at

1000 K passes through a heterogeneous magnetic ield having gradient of 300 T m−1 . It cov‑
ers a distance of 0.25 m in the magnetic ield. Calculate the separation between the traces.
(Mass of silver atom m = 1.79 × 10−25 kg, µB = 9.2 × 10−24 J T−1 , K = 1.38 × 10−23 J K−1 )
(Ans : 4.16 mm)

7. In the Stern–Gerlach experiment, silver atoms cover a distance of 0.4 m through an in‑
homogeneous magnetic ield of 200 T m−1 . The separation between the traces is 0.8 mm.
Calculate the velocity of silver atoms. (M = 1.79 × 10−25 Kg, µB = 9.2 × 10−24 J K−1 , K =
1.38 × 10−23 J K−1 ) (Answer: v = 1.43 × 103 m s−1 ).

8. In Stern–Gerlach experiment, silver atoms cover a distance of 0.12 m through an inho‑

mogeneous magnetic ield of gradient 50 T m−1 . The separation between the traces is
0.15 mm. Calculate the velocity of silver atoms. (Answer: 5 × 102 m s−1 )

9. A spectral line of frequency 8 × 1014 Hz in a magnetic ield of 40 T becomes triplet un‑

der normal Zeeman effect. Find Zeeman shift and component frequencies. (e = 1.6 ×
10−19 C, m = 9.1 × 10−31 kg) (Answer : 5.59 × 1011 Hz, 8.005 × 1014 Hz, 7.994 × 1014 Hz)