Let’s play physics 9681634157

Atomic And Molecular physics

Stern - Gerlach experiment.

The classic Stern-Gerlach Experiment shows that atoms have a property called spin. Spin is a kind of intrinsic angular momentum,
which has no classical counterpart. When the z-component of the spin is measured, one always gets one of two values: spin up or spin
down.

The space quantization of spin angular momentum of an electron was first demonstrated
by Stern Gerlach experiment.

Experimental method: Vaporized silver from the oven is converted in a thin beam of silver
by the slits and allowed to pass through inhomogeneous, transverse magnetic field,
generated by poles of strong magnet N,S. One pole is in the form of knife – edge while
other in form of channel to produce inhomogeneous magnetic field. The silver is finally
deposited on the photographic plate.

Observation: When the field is absent a thin straight line of silver is obtain; In the
presence of magnetic field the field splits into two separate lines.

Explanation: In a silver atom the outermost electron is in 2𝑠1 state. Hence there is only
2
𝑒ℏ
spin magnetic moment 𝜇𝑠 = = 𝜇𝐵 (𝐵𝑜ℎ𝑟 𝑚𝑎𝑔𝑛𝑒𝑡𝑜𝑛); Thus magnetic moment for Ag
2𝑚𝑒
atom is also 𝜇𝐵 .

⃗ the additional energy of the atom,

In the magnetic field of flux density 𝐵

⃗ = −𝜇𝑠 B cos 𝜃
𝐸 = −𝜇𝑠 ∙ 𝐵

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Now according to space quantization, the spinning electrons may orient either parallel or
anti parallel to the direction of applied magnetic field, i.e. 𝜃 = 𝑒𝑖𝑡ℎ𝑒𝑟 00 𝑜𝑟 1800 .

Hence 𝐸 = ∓𝜇𝐵 B

Here transverse force along z-axis will be,

𝑑𝐸 𝑑𝐵
𝐹𝑧 = = ∓𝜇𝐵
𝑑𝑧 𝑑𝑧

𝐹𝑧 𝜇𝐵 𝑑𝐵
Corresponding acceleration, 𝑎 = =∓ 𝑚, is the mass of single atom.
𝑚 𝑚 𝑑𝑧

Time taken by the atom to travel the length 𝑙 through the magnetic field with velocity
𝑙 1 𝜇𝐵 𝑑𝐵 𝑙 2 𝜇 𝑑𝐵
𝑣 is 𝑡 = . Hence transverse displacement 𝑑 = 𝑎𝑡 2 = ∓ 𝐵
( ) = ∓ 2𝑚𝑣 2 𝑑𝑧
𝑙2
𝑣 2 2𝑚 𝑑𝑧 𝑣

2𝑘𝑇
Considering ideal gas approximation, we have, 𝑣 (𝑚𝑜𝑠𝑡 𝑝𝑟𝑜𝑏𝑎𝑏𝑙𝑒) = √
𝑚

𝜇𝐵 𝑑𝐵 2
Hence, 𝑑 = ∓ 𝑙 .
4𝑘𝑇 𝑑𝑧

Separation on Photographic plate:- The path of the atomic stream within the non-
uniform magnetic field is the arc of a circle as shown in the figure. The tangent to
the arc at B, at the end of the field, meets at O, the mid point of the field strength.
The deflection from the original direction is D

𝑎
𝐷 +𝑙
2
From the geometry = 𝑎
𝑑
2

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1. Give a schematic description of the Stern-Garlach experiment and indicate its main
conclusions. Why was the experiment done with silver atoms? [6+1] [CU 2000, 2004]

The vector atomic model:- The two essential elements that characterise the vector atom
model are (i) Idea of space quantization (ii) the spinning electron hypothesis.

(i) Idea of space quantization:-According to Somerfield, the orbital plane of electron and
hence the orbital angular momentum 𝐿⃗ of the electron in the atom can be oriented in
space only in some limited number of special directions . These reference directions are
chosen as the direction of applied magnetic field.

For the possible orientations, the projection of 𝐿⃗ on the direction of applied field,

𝐿 cos 𝜃 = 𝑚𝑙 ℏ

𝜃 is the angle between 𝐿⃗ and the direction of the applied field and 𝑚𝑙 = 0, ±1, ±2, … . . ±𝑙 is
known as magnetic quantum number .
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(ii) The spinning electron:-In addition to the orbital motion the electron spins about its
own axis it possess spin angular momentum 𝑆 . According to the idea of space
quantization, spin angular momentum should also be quantised. Hence a new quantum
number spin quantum number s is introduced .
1
𝑖. 𝑒. 𝐿⃗ = 𝑠ℏ 𝑠=±
2

➢ Since the orbital and spin motions are both quantized in magnitudes and directions
they are considered as quantized vector and the atomic model based or these quantized
vectors is caused vector atomic model.

stern-gerlach_en.jar SternGerlachExperiment.cdf

Angular momentum and magnetic momentum:- Consider an electron of mass 𝑚 and charge
𝑒 rounds the nucleus of an atom in a circular or radius 𝑟 with a velocity 𝑣. The charge
circulating in a loop is equivalent a current,
𝑒𝑣
𝐼=− … … … . (𝑖)
2𝜋𝑟
Orbital magnetic moment of the electron

𝜇𝑙 = 𝑐𝑢𝑟𝑟𝑒𝑛𝑡 × 𝑎𝑟𝑒𝑎
𝑒𝑣
=− × 𝜋𝑟 2
2𝜋𝑟
𝑒𝑣𝑟
=− … … … (𝑖𝑖)
2
Now the orbital angular momentum of electron

𝐿 = 𝑟 × 𝑚𝑣 = 𝑚𝑣𝑟 [∴ path is ciru

The ratio of magnetic moment to the angular momentum is known as gyromagnetic ratio
on given as ,
𝜇 𝑒𝑣𝑟 𝑒
=− =− … … … (𝑖𝑖𝑖)
𝐿 2𝑚𝑣𝑟 2𝑚
𝑒
In vector notation 𝜇=− 𝑙 …………… (iv)
2𝑚

The −𝑣𝑒 𝑠𝑖𝑔𝑛 shows the direction of the magnetic moment is opposite to that of orbital
angular momentum.

➢ Bohr magneton :- According to Bohr’s theory, the angular momentum of the

electron is quantized in the unit of ℏ and given by.

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𝐿 = 𝑙ℏ

From equation (3) ignoring the sign,

𝑒
𝜇𝑙 = 𝑙ℏ
2𝑚
𝑒ℏ
= 𝑙
2𝑚
= 𝜇𝐵 𝑙
𝑒ℏ
Where 𝜇𝐵 = = 9.274 × 10−24 𝑗/𝑡𝑒𝑠𝑙𝑎 this is known as Bohr magneton, the basic unit
2𝑚
of atomic magnetic moment.

➢ Spin angular momentum and magnetic moment :- Due to the spinning motion of the
⃗⃗⃗𝑠 and spin magnetic moment. 𝜇𝑠
electron it spins an intrinsic spin angular momentum 𝑃

However the ratio of 𝜇𝑠 to 𝑆 is different from the gyromagnetic ratio for orbital motion
𝜇𝑠 𝑒
and is given by . = 𝑔𝑠
𝑝𝑠 2𝑚

𝑔𝑠 is known as lande- g- factor and here 𝑔𝑠 = 2 (for electron)

𝑒
∴ 𝜇𝑠 = 2. 𝑃
2𝑚 𝑠
𝑒
= 2. 𝑠ℏ
2𝑚
1
Since 𝑣 ke 𝐿, 𝑆 is also quantized and given by 𝑆 = 𝑠ℏ 𝑤ℎ𝑒𝑟𝑒 𝑠 =
2

𝑒 1
Magnitude of spin magnetic moment 𝜇𝑠 = . ℏ
𝑚 2

𝑒ℏ
= = 𝜇𝐵
2𝑚

So spin magnetic moment of the electron is equal to Bohr magneton.

➢ Quantum numbers associated with the vector atom model :-

1.rincipal quantum number(n) :- It is symbolised by 𝑛 and is an integer that can take up

values 1.2.3 … ∝ and corresponds to 𝑛 of Bohr Somerfield theory. It determines the size
of the electronic orbit and arises from quantization of the energy of the electron .

2.The orbital quantum number (l):-this is repress by 𝑙 . It is also an integer that can for a 𝑛
takes up values 0,1,2,……𝑛 − 1. It arises from quantization of the magnitude of orbital
angular momentum 𝐿 of the electron and is given by √𝑙(𝑙 + 1)ℏ
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By convention the electron is called , 𝑠, 𝑝, 𝑑, 𝑓 etc electron according as 𝑙 = 0,1,2,3, … .. etc.

The 𝑙 value determines the shape of the orbit.

1
3.The spin quantum number(s):-This is symbolized by s .It always takes the value for
2
electron , arises from quantization of the magnitude of the spin angular momentum ⃗S and
given by S = √𝑠(𝑠 + 1)ℏ

In absence of any external field the motion the electron can be completely described in
terms 𝑛, 𝑙 and 𝑆

4.Total angular momentum number :-This is symbolized by 𝐽 and is the vector sum of the
1
quantum numbers 𝑙 and 𝑆. Since 𝑆 is always , 𝐽 = 𝑙 + 𝑆 = 𝑙 ± 1⁄2 (+) sign is when 𝑆 is
2
parallel to 𝑙 and are where 𝑆 is anti parallel . This total angular momentum is given by 𝐽 =
√𝐽(𝐽 + 1)ℏ.

5.Magnetic orbital quantum number :- A magnetic field has a directive in fluency on orbital
motion of the electron magnetic orbital quantum number 𝑀2 has for a given 𝑙 (2𝑙 + 1)
integral values from −𝑙 to 𝑙 as 𝑚2 = 𝑙, 𝑙 − 1, 𝑙 −
2, … .0 … 1, −2. . (𝑙 − 1), −𝑙

It arises from the quantization of the direction of the

angular momentum L and determines the orientation of
the orbit in space.

For the angle 𝜃 between applied field and angular

𝑚
momentum, the direction are given by cos 𝜃 = 𝑙
𝑙
𝑚𝑙
quantum mechanicall , cos 𝜃 = space quantization
√𝑙(𝑙+1)
represented for 𝑙 = 3 in the above fig.

6. Magnetic spin quantum number:- A magnetic field also has a directive influence on spin
1 1
motion of the electron. Magnetic spin quantum number 𝑚𝑠 has values and − . It arises
2 2
from quantization of the spin angular momentum S and determines the orientation of the
opine either up or down this is shown in the adjacent figure.

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7.Total magnetic quantum number:-It is the projection of total angular momentum vectore
𝑗 on the direction of the magnetic field this can take the values as

𝑚𝑗 = 𝑗, 𝑗 − 1. .0, −1, −2 … 𝑏 − 1, −𝑗

➢ If 𝑛, 𝑙, 𝑚2 and 𝑚𝑠 are known 𝑗 and 𝑚𝑗 could found and the electron in an atom is
complete defined.
⃗ is applied, it interacts with the
➢ Larmor precession :- When an external magnetic field 𝐵
orbital magnetic moment 𝜇 and a torque acts as,
𝜏 =𝜇×𝐵 ⃗ = − 𝑒 𝐿⃗ × 𝐵
⃗ = 𝑒 𝐵⃗ × 𝐿⃗ 𝐿⃗ = corresponding
2𝑚 2𝑚
angular momentum.
⃗⃗⃗⃗
𝑑𝑙
However 𝜏 = ;
𝑑𝑡
⃗⃗⃗⃗
𝑑𝑙 𝑒
∴ = ⃗ × 𝐿⃗
𝐵
𝑑𝑡 2𝑚

But the magnitude of angular momentum {√𝑙(𝑙 + 1)ħ } and also the
angle θ between 𝐿⃗ and 𝐵
⃗ do not change; so only the azimuthal
angle ∅ will change due to the torque. This causes precision i.e. 𝐿⃗
moves on the surface of a cone now.

Let 𝑑∅ be the angle that 𝑑𝐿⃗ subtends at the point where 𝐵

⃗ passes through the plane of
⃗|
|𝑑𝐿
precession ∴ from the fig 𝑑∅ =
𝐿 sin 𝜃

The angular velocity of precession,

𝑑𝐿⃗
| |
⃗⃗⃗ × ⃗⃗⃗⃗
𝑑∅ 𝑑𝑡𝑒 |𝐿 𝐵| 𝑒 𝐿𝐵 sin 𝜃 𝑒
𝜔𝑝 = = = = = 𝐵
𝑑𝑡 𝐿 sin 𝜃 2𝑚 𝐿 sin 𝜃 2𝑚 𝐿 2𝑚
𝑒
∴ Frequency of Larmour precession 𝑓 = 𝐵
4𝜋𝑚

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⃗ and ⃗𝑺 :-The angular momenta 𝐿⃗ and 𝑆 interact magnetically and
Precession of 𝑱 ,𝑳
produce total angular momentum 𝑗 . If there is no external magnetic field, 𝑗 is conserved
in magnitude and direction and the effect of internal torques is the precession of 𝐿⃗ and 𝑆
about 𝐽 [fig-1].

⃗ and 𝐿⃗, 𝑆 continues processing about 𝐽

In presence of magnetic field 𝐽 precesses about 𝐵
[fig.2]

AdditionOfAngularMomentaInQuantumMechanics (1).cdf

➢ Spin 0rbit interaction :- The energy levels of atomic electrons are affected by
interaction between the electron spin magnetic moment and the orbital magnetic
moment of the electrons. It can be visualized as a magnetic field caused by the electron
orbital motion, interacting with the spin magnetic moment .
This in term of angular momentum we can say all electrons (or electron) having spin
angular momentum 𝑆, interact with the orbital angular momentum 𝐿⃗; and this
addition of angular momentum gives rise to total angular momentum 𝐽 . 𝐽 = 𝐿⃗ + 𝑆
For single electronic system 𝐽 = 𝐿⃗ + 𝑆 =𝐿⃗ ± 1⁄2 ℎ. Obeying vector addition rule.
The allowed values of the total angular momentum quantum number j, given two
angular momenta corresponding to quantum numbers +𝑗2 are: 𝑗 = 𝑗1 + 𝑗2 , 𝑗1 +
𝑗2 − 1, . . . , |𝑗1 − 𝑗2 | and for each of these values of j, m takes on the (2j + 1) values m
= j, j − 1,..., −j .
The proof of this theorem is beyond the scope of these lectures, and is deferred to more advanced courses.

➢ Spectroscopic notation :- A spectroscopic rotation in atomic physics is a common way

to name the states. It is a standard way to write down the angular momentum quantum
numbers.
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2𝑠+1
The general form is = 𝑛 𝑋𝐽 ,
• X refers to orbital quantum numbers 𝑙 written as 𝑙 => 𝑆(0), 𝑃(1), 𝐷(2), 𝐹(3)
• S is total spin quantum no [(2𝑠 + 1)denotes the number of spin states]
• J is the total orbital quantum numbers.
• N is principal quantum numbers [often is omitted]

For 32 𝑑 5⁄2 state find 𝑛 , 𝑙, 𝑠, 𝑗 :-The energy levels in atomic spectroscopy are
labelled as

𝑛2𝑠+1 𝑋𝐽 Here 𝑛 = 3

𝑋=𝐷=2
2𝑠 + 1 = 2
𝑠 = 1⁄2 [Since it is a single electronic system
𝑗 = 5⁄2 alphabets are taken in small latter]
➢ Calculate the values of 𝒍 , 𝒔 , 𝒋 and 𝒍, 𝒔
⃗ , 𝒋 for a p electron in n principle stats :-

For p electron 𝑙 = 1
1
for single electron and 𝑠 =
2

3 1
∴ Possible 𝑗 values are 𝑗 = 𝑙 ± 𝑠 = ,
2 2

∴ Two states are can be formed ,as 𝑛2𝑠+1 𝑃𝑗

(i) 32 𝑝𝑛⁄2 (ii) 32 𝑝1⁄

2

𝐿⃗ = √1(1 + 1) ℏ =) √2ℏ;

1 1 √3
𝑆 = √ (1 + ) ℏ; = ℏ
2 2 2

3 3 1 1
𝑗 = √ (1 + ) ℏ, √ (1 + ) ℏ
2 2 2 2

√12 √3
= ℏ; ℏ,
2 2

➢ Coupling schemes :- In an atom having more than one optically active electrons, the
orbital spin angular momenta of all its electron be added together to give the total
angular momentum .the method of combination depend on the interaction or coupling
between the orbital and spin angular momentum .
➢ two types of schemes has been developed

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(i)L-S or Russel-Sauders coupling (ii) the J-J coupling

(i) L-S coupling: - In most of the atoms excepting heavier one, all the orbital angular
momentum vectors of various electrons combine to form a resultant 𝐿⃗ . Independently all
their spin angular momenta vectors combine to form a resultant 𝑆 .These resultant 𝐿⃗ and
𝑆 then combine to form the total angular momentum 𝐽 of the atom .

The scheme can be summarised as,

𝐿⃗ = 𝐿⃗1` ⨁ 𝐿
⃗ 2 ⨁ +∙∙∙∙∙∙= ∑ 𝐿⃗

𝑆 = 𝑆1 ⨁ 𝑆2 ⨁ +∙∙∙∙∙∙∙∙= ∑ 𝑠𝑖

𝐽 = 𝐿⃗⨁𝑆

If 𝐿𝑖 and 𝑆𝑖 be orbital and spin quantum number of individual

electron then

𝐿⃗𝑖 = √𝑙𝑖 (𝑙𝑖 + 1)ℏ

𝑆𝑖 = √𝑠𝑖 (𝑠𝑖 + 1)ℏ

If L and S be total orbital and total spin quantum numbers

then

𝐿⃗ = √𝐿(𝐿 + 1)ℏ

𝑆 = √𝑆(𝑆 + 1)ℏ

For 2 electron system

𝐿 = (𝑙1 + 𝑙2 ) ⋅⋅⋅⋅⋅⋅ (𝑙1 + 𝑙2 − 1) ⋅⋅⋅⋅⋅⋅⋅ (𝑙1 + 𝑙2 )

Or 𝑆 = (𝑆1 + 𝑆2 ) ⋅⋅⋅⋅⋅⋅ (𝑆1 + 𝑆2 − 1) ⋅⋅⋅⋅⋅⋅⋅ (𝑆1 + 𝑆2 )

For total angular momentum if J total angular quantum number; 𝐽 = √𝑗(𝑗 + 1)ℏ

Possible J values are =(𝐿 + 𝑆), (𝐿 + 𝑆 − 1) ∙∙∙∙∙∙∙ (𝐿 − 𝑆)[𝐿 > 𝑆] or

(𝑆 + 𝐿), (𝑆 + 𝐿−) ⋅⋅⋅⋅⋅⋅ (𝑆 − 𝐿)[𝑆 > 𝐿]

➢ let us consider the L-S coupling of a 3𝑝 electron with a 4𝑑 electron

here 𝑙1 = 1 𝑎𝑛𝑑 𝑙2 = 2
1 1
𝑆1 = 𝑎𝑛𝑑 𝑆2 =
2 2
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∴ Possible values of 𝐿 = 3,2,1,

Possible values of 𝑆 = 1,0

possible values of 𝐽 = |𝐿 + 𝑆|, |𝐿 + 𝑆 − 1| ∙∙∙∙∙∙∙∙∙∙ |𝐿 − 𝑆|

possible configurations with their spectral notation is listed below

S L J Spectral notation of the terms 2𝑠 + 1(𝑙)𝑗

3 4, 3 , 2 3𝐹4 , 3𝐹3 , 3𝐹2

1 2 3, 2 , 1 3𝐷3 , 3𝐷2 , 3𝐷1

1 2, 1, 0 3𝑃2 , 3𝑃1 , 3𝑃0

3 3 1𝐹3

0 2 2 1𝐷2

1 1 1𝑃1

What will happen if both the electron were belong to am principal q no.

(ii) J-J coupling :- This type of coupling exists mostly in heavy atoms. Here the interaction
between the spin and orbital vectors of each electron is stronger than the interaction
between either the spin vector and the orbital vector of different electron.

The orbital and spin angular momenta of each atom are added and produce resultant
angular momentum 𝐽𝑖 = 𝑙𝑖 + 𝑠𝑖 ; The vector sum of all the individual ⃗𝑗𝑖 vectors gives the
total angular momentum 𝐽 of the atom. Thus, ⃗𝑗 = ∑ ⃗𝑗𝑖

➢ let us consider the J-J coupling of a 𝑛 − 𝑝 electron with 𝑛 − 𝑑 electron

1 3 1
for p- electron 𝑙1 = 1 𝑆1 = ∴ 𝑗1 = ,
2 2 2
1 5 3
for d- electron 𝑙2 = 2 𝑆1 = ∴ 𝑗2 = ,
2 2 2
The four J-J combination gives the following J values
1 3
𝐽1 = , 𝐽2 = 𝐽 = 2, 1
2 2
1 5
𝐽1 = , 𝐽2 = 𝐽 = 3, 1
2 2

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3 3
𝐽1 = , 𝐽2 = 𝐽 = 3,2, 1,0
2 2
3 5
𝐽1 = , 𝐽2 = 𝐽 = 4,3,2, 1
2 2
The four states are written as,
1 3 1 5 3 3 3 5
( , ) ( , ) ( , ) ( , )
2 2 2,1 2 2 3,2 2 2 3,2,1,0 2 2 4,3,2,1

➢ The Lande –g- factor :- The magnetic moment of the electron in an atom arises due to
its orbital motion around the nucleus as well as due to its spin .
𝑒
The orbital magnetic moment 𝜇𝑙 = − (
2𝑚
) 𝐿⃗

𝑒
And that due to spin is, 𝜇𝑠 = −2 ( )𝑠
2𝑚

𝑒
∴ Total magnetic moment of electron 𝜇𝑙𝑠 = 𝜇𝑙 + 𝜇𝑠 = − (𝑙 + 2𝑠)
2𝑚

∴ We define total angular momentum vector 𝑗 = 𝑙 + 𝑠

𝑒
∴ 𝜇𝑙𝑠 = − (𝑗 + 𝑠)
2𝑚
The figure shows the geometrically the relationship between angular momentum vectors
and magnetic momentum vectors.

The resultant magnetic moment 𝜇𝑙𝑠 (= 𝜇𝑙 + 𝜇𝑠 ) is not along the line of vector 𝐽. Since 𝐿⃗, 𝑆
precess about 𝐽 ; 𝜇𝑙 and 𝜇𝑠 also process about 𝐽 hence their resutant 𝜇𝑙𝑠 also process about
𝑗.

The effective magnetic moment of the electron will therefore be 𝜇𝑗 the component of 𝜇𝑙𝑠
along the direction of 𝑗 ( −𝑗)
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The component perpendicular to 𝑗 will be zero on average ,over one complete revolution
and 𝜇𝑗 may be written as .
𝑗
𝜇𝑗 = (𝜇𝑙𝑠 . 𝑗̂)𝑗̂ where 𝑗̂ is unit vector 𝑗̂ =
𝐽
(𝜇𝑙𝑠 . 𝑗)𝑗
=
𝐽2

𝑒 (𝑗 + 𝑆). 𝑗
= − 𝐽
2𝑚 𝐽2
𝑒
= − (𝑔) 𝑗
2𝑚
Here,
𝐽2 + 𝐽. 𝑆 𝐽. 𝑆
𝑔= = 1 +
𝐽2 𝐽2
Since, 𝐿⃗ = 𝐽 − 𝑆
∴ 𝐿2 = 𝐽2 + 𝑆 2 − 2𝐽. 𝑆

𝐽2 + 𝑆 2 − 𝐿2
𝑜𝑟 𝑗 . 𝑆 =
2𝐽2
𝐽 + 𝑆 − 𝐿2
2 2
∴ 𝑔 = 1+
2
𝐽2 + 𝑆 2 − 𝐿2
= 1+
2𝐽2
Replacing 𝐽2 , 𝑆 2 , 𝐿2 by their quantum mechanical values 𝐽(𝐽 + 1), 𝑆(𝑆 + 1), 𝐿(𝐿 + 1),
𝐽 (𝐽 + 1) + 𝑆(𝐽 + 1) − 𝐿(𝐿 + 1)
𝑔 = 1+
2𝐽(𝐽 + 1)

The quantity 𝑔 is called land – 𝑔- factor. Its values depends on the quantum numbers
𝐿 , 𝑆 , 𝐽 it value is different for different states .

Total magnetic moment of the electron as

𝑒 𝑒 𝑒ℏ
𝜇𝑗 = − 𝑔𝑗 = − 𝑔√𝐽 (𝐽 + 1) ℏ = − 𝑔√𝐽 (𝐽 + 1) = −𝜇𝐵 𝑔√𝐽 (𝐽 + 1)
2𝑚 2𝑚 2𝑚

➢ Calculate the lande –g- factor and the total magnetic moment for flowing g states
2
(a) 𝑆1 (𝑏) 2𝑃1 (𝑐) 2𝑃3 (𝑑) 2𝐷1
2 2 2 2

Sol.- (a) For the state 2𝑆1

2

𝑙 = 0 , 𝑗 = 1⁄2 , 2𝑆 + 1 = 2 𝑜𝑟 𝑆 = 1⁄2
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(𝐽 + 1) + 𝑆 (𝑆 + 1) − 𝐿(𝐿 + 1)
𝑛𝑜𝑤 𝑔 = 1+ 𝐽
2 𝐽(𝐽 + 1)

3 3
+ −0
= 1 + 4 4
2 . 3⁄4

=1+1

=2

∴ Total magnetic moment

𝜇𝑗 = 𝑔 √𝑗(𝑗 + 1)𝜇𝐵

1 3
= 2 √ ∙ 𝜇𝐵
2 2

= √3𝜇𝐵

Calculate (B), (c) ,(d)(Answers are given);

2 4 4
(b) 𝑔 = (𝑐) 𝑔 = (𝑑) 𝑔 =
3 3 5

1 2 2
𝜇𝑗 = 𝜇𝑏 𝜇𝑗 = √1𝑠 𝜇𝑏 𝜇𝑗 = 𝜇𝑗 = √1𝑠 𝜇𝑏
√3 3 3

➢ For single electron 𝑔 = 2; calculate it.

➢ In a many electron atom the orbital spin and total angular momentum are 𝑙 = 2, 𝑠 =
−1
1, 𝑗 = 2 Find the angle between ⃗𝑙, 𝑠 [𝑐𝑜𝑠 −1 ]
√12

➢ The ground state of chlorine atom is 2𝑃3 calculate the magnetic

2
dipole moment
10
ℎ𝑖𝑛𝑡 => 𝑓𝑖𝑛𝑑 𝑔 (= 1 + )
30

∴ 𝜇𝑗 = −𝑔 𝜇𝑏 √𝑗 (𝑗 + 1)

2
= − √15 𝜇𝑏
3

➢ Angle between 𝐿⃗ 𝑎𝑛𝑑 𝑆:

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We have 𝑗 = 𝐿⃗ + 𝑆
∴ 𝑗 2 = 𝑙 2 + 𝑠 2 + 2𝐿⃗ ∙ 𝑆

= 𝑙 2 + 𝑠 2 + 2 𝑙 𝑠 cos 𝜃

𝑗2 − 𝑙2 − 𝑠2
∴ cos 𝜃 =
2𝑙𝑠
𝑗(𝑗 + 1) − 𝑙 (𝑙 + 1) − 𝑠(𝑠 + 1)
=
2√𝑙(𝑙 + 1) √𝑠(𝑠 + 1)

➢ Similarly considering, 𝑠 = 𝑗 − 𝑙 𝑎𝑛𝑑 𝑙 = 𝑗 − 𝑠 it can be shown,

Angle between 𝑗, 𝑙 il cos( 𝑗, 𝑙 )

𝑗(𝑗 + 1) + 𝑙 (𝑙 + 1) − 𝑠(𝑠 + 1)
cos (𝑗, 𝑙 ) =
2√𝑗(𝑗 + 1) √𝑙(𝑙 + 1)

Angle between 𝑗, 𝑠
𝑗(𝑗 + 1) + 𝑠 (𝑠 + 1) − 𝑙(𝑙 + 1)
cos (𝑗, 𝑆) =
2√𝑗(𝑗 + 1) √𝑠(𝑠 + 1)

3
➢ Evaluate the Lande 𝑔 factor for 𝑃1 level. Use this result to prediet the splitting in eV ,

of the levels when the atom is in an external magnetic field of 1T . Given Bohr magneto
𝑗
=9 ∙ 3 × 10−𝑡 ⁄𝑡 .

For 3𝑃1 level 𝐿 = 1

∴ (2S+1)=3 ∴ 𝑆 = 1

𝐽=1

𝐽(𝐽 + 1) + 𝑆(𝑆 + 1) − 𝐿(𝐿 + 1)

∴ 𝑔 =1+
2 𝐽(𝐽 + 1)
1
=1+
2
3
=
2
Now ∆∈ = 𝜇𝐵 𝑔𝑗 𝑚𝑗 𝐵

3
= 𝑚𝑗 ∙ (9 ∙ 3 × 10−24 )0 ∙ 1
2
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= 𝑚𝑗 .1 ∙ 392 × 10−24 𝑗

= 𝑚𝑗 8 ∙ 27 × 10−6 𝑒𝑣

For 𝑚𝑗 = 1, ∆∈= 8 ∙ 27 × 10−6 𝑒𝑣

𝑚𝑗 = 0 ∆∈= 0

𝑚𝑗 = 1, ∆∈= −8 ∙ 27 × 10−6 𝑒𝑣

➢ Explain the origin of Na 𝑫𝟏 , 𝑫𝟐 lines :-The D line of Na atom originates from transition
3𝑝 → 3𝑠 [called principal series]
1 3 1
For 3𝑝 state, 𝑙 = 1, 𝑠 = , 𝑗= −
2 2 2

1 1
For 3𝑠 state 𝑙 = 0 𝑠 = ; 𝑗=
2 2

∴ Energy level diagram . 𝐷1 𝐷2

Zeeman effect :- It is an magneto optical phenomena first discovered by Zeeman . It was

observed that if a source of light producing line spectrum, is placed in strong magnetic
field ,that spectra lines are spit into fine structures. Zeeman effect is often classified as
(i) Normal Zeeman effect (ii) anomalous Zeeman Effect

Normal Zeeman effect:- The splitting of a spectral line into three components in a
magnetic field when viewed in a direction perpendicular to that of magnetic field , it is
known as normal Zeeman effect [when the spectral line is examined parallel to applied
field each line appear to split into two equidistant lines from original line .They are
circularly polarized in opposite sense]

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➢ Explanation of normal Zeeman effect :- The space quantization of electron orbit

provides a satin factory explanation of normal Zeeman effect. Let an atom having orbital
angular momentum 𝐿⃗ only, be placed in an external magnetic field 𝐵⃗ along z.

The interaction energy ∆∈ of the atom due to interaction between magnetic field
⃗ = 𝐵𝑧̂ ) and magnetic moment 𝜇𝑙 ,
(𝐵

⃗
∆∈ = −𝜇𝑙 ∙ 𝐵

Now magnetic moment in term of angular momentum 𝐿⃗, ,

𝑒
𝜇𝑙 = − 𝐿⃗
2𝑚
𝑒
⃗ =
∆∈ = −𝜇𝑙 ∙ 𝐵 𝐵𝐿⃗ ∙ 𝑧̂
2𝑚
𝑒
= 𝐵𝐿
2𝑚 𝑍
𝑒ℏ
= 𝑚𝑙 ( )𝐵
2𝑚
= 𝑚𝑙 𝜇𝐵 𝐵

Now the energy of the electronic state 𝐸𝑛𝑙𝑚 = 𝐸𝑛𝑙 + 𝑚𝑙 𝜇𝐵 𝐵

Since 𝑚𝑙 can have (2𝑙 + 1) values from to 𝑙[−𝑙, −(𝑙 − 1) … .0 … . (𝑙 − 1)𝑙] the energy can
have (2𝑙 + 1) each slightly different values each determined by 𝑞 𝑛𝑜 𝑚𝑙 .

Now any transition between two subshell governed by selection rule ∆𝑙 = ±1 will be
controlled by the selection rule ∆𝑚, = 1,0, −1

Considering the transition between the initial and find energy levels 𝐸𝑙 , &𝐸𝑓 where

𝐸𝑖 = 𝐸𝑛𝑖𝑙𝑖 + (𝑚𝑙 )𝑖 𝜇𝐵 𝐵
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& 𝐸𝑓 = 𝐸𝑛𝑓𝑙𝑓 + (𝑚𝑙 )𝑓 𝜇𝐵 𝐵

∆𝐸 = 𝐸𝑖 − 𝐸𝑓

𝑜𝑟 ℎ𝛾 = (𝐸𝑛𝑖𝑙𝑖 − 𝐸𝑛𝑓 𝑙𝑓 ) + ∆𝑚𝑙 𝜇𝐵 𝐵

𝐸𝑛𝑖 𝑙𝑖 − 𝐸𝑛𝑓𝑙𝑓 𝜇𝐵 𝐵
𝛾 = + ∆𝑚𝑙
𝛾 ℎ
𝑒𝐵
= 𝛾0 + ∆𝑚𝑙 = 𝛾0 + 𝑚𝑙 ∆𝛾
4⌅𝑚
𝛾0 is the frequency of initial line since ∆𝑚𝑙 = 0, ±1

𝛾 = 𝛾0 𝑤ℎ𝑒𝑛 ∆𝑚𝑙 = 0

𝛾 = 𝛾0 + ∆𝛾 ∆𝑚𝑙 = 1

𝛾 = 𝛾0 − ∆𝛾 ∆𝑚𝑙 = −1

[splitting of energy levels in magnetic field and possible transition ]

➢ Anomalous Zeeman effect :- The splitting of spectral line in a weak magnetic field
shows in general more than three lines as observed in normal Zeeman effect this type of
complex splitting due to existence of electron spin is called anomalous Zeeman effect.

The anomalous Zeeman effect can be explained on the basis of vector atomic model
considering the electron spin in addition to the orbital motion of the electron.

The magnetic moment of the electron in an atom rises due to its orbital motion

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∴ Total magnetic moment of the electron,
𝑒
𝜇𝑗 = − 𝑔𝑗
2𝑚
𝑒
=− 𝑔√𝑗(𝑗 + 1)ℏ
2𝑚
Splitting of energy levels :- In a weak magnetic field the energy due to external magnetic
field is small compare to spin orbit coupling.

⃗ 0 with the system,

The interaction energy of 𝐵

⃗
∆𝐸 = −𝜇𝑗 ∙ 𝐵
𝑒
= ⃗
𝑔 𝑗. 𝐵
2𝑚
𝑒𝐵
=𝑔 𝑗. 𝑧̂ 𝑧 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑜𝑓 𝑗 → 𝑗𝑧 = 𝑚𝑗ℏ
2𝑚

𝑒𝐵
=𝑔 𝐽
2𝑚 𝑧
𝑒𝐵
=𝑔 𝑚𝑗 ℏ = 𝑔𝑚𝑗 𝜇𝐵 𝐵
2𝑚

For a particular 𝐽 , 𝑚𝑗 can have 𝑗, 𝑗 − 1 … . .0 … . 𝑗 𝑖. 𝑒. (2𝑗 + 1) number of values and give

rise to magnetic splitting of spectral lines .The separation depends on product 𝑔𝑚𝑗 .

=> we consider the transition between the energy levels 𝐸𝑖 ; 𝐸𝑓 where.

𝐸𝑖 = (𝐸0 )𝑖 + 𝑔𝑖 (𝑚𝑗 )𝑖 𝜇𝐵 𝐵

𝐸𝑓 = (𝐸0 )𝑓 + 𝑔𝑓 (𝑚𝑗 )𝑓 𝜇𝐵 𝐵

∴ emitted frequency,

𝐸𝑖 − 𝐸𝑓 (𝐸0 )𝑖 − (𝐸0 )𝑓 𝑔𝑖 (𝑚𝑗 )𝑖 − 𝑔𝑓 (𝑚𝑗 )𝑓

𝛾= = +[ ] 𝜇𝐵 𝐵
ℎ ℎ ℎ

𝜇𝐵 𝐵
= 𝛾0 + ∆(𝑔𝑚𝑗 )
ℎ
The transition between the magnetically split levels are controlled by selection rule,

∆𝑙 = ±1,

∆𝑚𝑗 = 0 ± 1

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[A gain 𝑔 the lande 𝑔 factor depends on 𝑙, 𝑠, 𝑗 values of each of the state and hence
different γ are obtained even for same ∆𝑚 unlike normal Zeeman Effect]

Example with Na –D lines:-Let us consider the magnetic splitting of Na –D line (𝐷1 , 𝐷2 )

𝐷1 and 𝐷2 lines originate due to following transitions,

𝐷1 𝑙𝑖𝑛𝑒 ∶ 32 𝑝1⁄ → 32 𝑠1⁄

2 2

𝐷1 𝑙𝑖𝑛𝑒 ∶ 32 𝑝3⁄ → 32 𝑠1⁄

2 2

The values of 𝑔, 𝑚𝑗 and (𝑔𝑚𝑗 ) are listed below with corresponding 𝐿, 𝑆, 𝐽

Levels L S J 𝑔𝑗 𝑚𝑗 𝑔𝑗 𝑚𝑗

3 ±2
±
1 3 4 2
32 𝑝3 1
2 2 2 3 1 2
± ±
2 3

32 𝑝1 1 1 2 1 1
1 ± ±
2 2 2 3 2 3

32 𝑠1 1 1 1
0 2 ± ±1
2 2 2 2

The
splitting of the levels and the allowed transition are shown below.
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➢ Explain why normal Zeeman effect occurs only in atoms with even no of electron in
outer most shell. Which of the elements H; 𝑯𝐞 Li Mg Na might exhibit normal Zeeman
effect,
Normal Zeeman effect occurs only in the atom with spin 𝑆 = 0 so that spin magnetic
moment is zero .Under this condition total angular momentum 𝐽 is equal to L and the
transitions between the subshell are characterized by the selection rule ∆𝑚𝑙 = 0, ±1
Now ′𝑠′, to be zero , number of electrons in the outermost valance orbit should be
even.
Here the electron configure of the atoms.
𝐻 → 1 𝑠1
𝐻𝑒 → 1 𝑠 2
𝐿𝑖 → 1 𝑠 2 2𝑠1
𝑁𝑎 → 1 𝑠 2 2𝑠 2 2𝑝6 3𝑠1
𝑀𝑔 → 1 𝑠 2 2𝑠 2 2𝑝6 3𝑠 2

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Molecular spectroscopy
Diatomic molecules – rotational and vibrational energy levels. Basic ideas about molecular
spectra. Raman effect and its application to molecular spectroscopy (qualitative discussion only).

PURE ROTATIONAL SPECTRUM OF A DI-ATOMIC MOLECULE.

This spectrum arises from transition involving changing rotational energy (Er) of the
molecules having permanent dipole moment. We consider the vibrational and electronic
energy of the molecule remains unchanged while the molecule rotates under applied
electric field.

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Let m1 , m2 be the masses of two atoms joined by a rigid bond of length r0 (=r1+r2)
r1,r2 being the distances of the masses m1 , m2 from the centre of mass c.m.
∴𝑚1 𝑟1 = 𝑚2 𝑟2 = 𝑚2 (𝑟0 − 𝑟1 )
𝑚2
Or, r1 = r0
𝑚1 +𝑚2
𝑚1
Similarly we can have, r2 = r0
𝑚1 +𝑚2
Moment of inertia of the system about the axis of rotation ,
𝑚2 𝑚1 2
I = 𝑚1 (
𝑚1 +𝑚2
) 𝑟02 + 𝑚2 (𝑚 ) 𝑟02
1 +𝑚2
𝑚1 𝑚2
=(𝑚1 + 𝑚2 ) (𝑚 )
𝑟2
2 0
1 +𝑚 2
𝑚 𝑚2
=(𝑚 1 𝑟02 ;
1 +𝑚2 )
=𝜇𝑟02 ;
𝑚 𝑚2
𝜇 = (𝑚 1 , is the reduced mass of the system.
1 +𝑚2 )
Thus the rotation can be viewed as the rotation of a point mass 𝜇 about an axis, with
radius 𝑟0 .

𝐿2
Kinetic energy of rotation 𝐸𝐾 = ,
2𝐼
Angular momentum 𝐿 can have quantum mechanical value 𝐿 = √𝑗(𝑗 + 1)ℏ; j is called
‘rotational quantum number’ , can have values 1,2,3,4…….
The molecule can thus have a discrete set of rotational energy levels , each corresponds
to a given j- value .Hence the quantized rotational energy levels,
ℏ2
𝐸𝐽 = 𝑗(𝑗 + 1) .
2𝐼
The allowed transitions between the energy levels are governed by the selection rule
∆𝑗 = ±1
Let us consider a transition from 𝑗th level to (𝑗 + 1)th level.
Change in rotational energy for this transition ,
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ℏ2 ℏ2
∆𝐸𝑗 = 𝐸𝑗+1 − 𝐸𝑗 = (𝑗 + 1)(𝑗 + 2) − 𝑗(𝑗 + 1)
2𝐼 2𝐼
ℏ2
= 2(𝑗 + 1)
2𝐼
ℎ2
= 2(𝑗 + 1)
8𝜋2 𝐼
Expressing in term of wave number of the emitted radiation,
1 ∆𝐸𝑗
𝜈̅𝑗 = ( ) = ,
𝜆 𝑗 ℎ𝑐
ℎ
= 2(𝑗 + 1)
8𝜋2 𝐼𝑐
= 2 B(𝑗 + 1).
ℎ
𝐵 = , is called rotational constasnt.
8𝜋2 𝐼𝑐
The rotational energy levels and the allowed transition between the energy levels with the
spectrum is shown below,

Thus the pure rotational spectrum of a rigid atomic molecule consists of a series of
equally spaced lines , having spacing 2B in wave number.

Prob : Calculate the equilibrium bond length for CO molecule for which the wave no. difference between two
successive lines in pure rotational spectrum is 3.842𝑐𝑚−1 .

According to this problem difference between two successive lines

2B =3.842𝑐𝑚−1

B = 1.921 𝑐𝑚−1 = 192.1 𝑚−1

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ℎ
Again 𝐵 =
8𝜋2 𝐼𝑐

ℎ 6.626×10−34
I= = =1.456 × 10−46 kg-m2
8𝜋2 𝐵𝑐 8×𝜋2 ×3×108 ×192.1

Reduced mass of CO ,
𝑚 𝑚𝑂 𝑀 𝑀𝑂 1
𝜇 = (𝑚 𝐶 )
= (𝑀
𝐶
)
×
𝐶 +𝑚𝑂 𝐶 +𝑀𝑂 𝑁𝐴

𝑀𝐶 at. mass of carbon =12

𝑀𝑜 at. mass of oxyzen = 16

𝑁𝐴 Avogadro’s no=6.023×1023
12×16 1
𝜇= (12+16)
× = 1.318 ×10−23 gm.
6.023×1023

= 1.318 ×10−26 kg.

Since I= 𝜇𝑟02

𝐼 1.456 ×10−46
𝑟0 = √ = √
𝜇 1.318 ×10−26

= 1.13×10−10 m

= 1.13 A0
Q: why all the molecules do no response in rotational spectroscopy?

Since the emission of radiation is due to the rotation of dipole moment, hence the
molecules having electric dipole moment can absorb or emit electro- magnetic radiation
hence response in rotational spectroscopy.

In case of polar molecules like HCl, CO, consists of unlike atoms (different electro --
negativity ), centre of +ve and –ve charges are permanently separated so that
permanent dipole moment is formed .Hence response in rotational spectroscopy . But the
molecules like O2 , CO2 are symmetric ,non- polar , i.e they do not have permanent dipole
moment. Thus they do not exhibits rotational spectra.

INTENSITIES OF ROTATIONAL LINES : The intensities of rotational spectra line depend

on the relative probability of transitions between the rotational energy levels ,which again
depends on the following s
i) Boltzmann factor, giving the relative number of molecules in the different initial
rotational energy states.

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If N be the number of molecules in the lowest energy state , j=0, then the number of
molecule in the jth state will be ,

−𝐸𝐽
𝑁𝐽 = 𝑁0 𝑒 𝐾𝑇 𝐸𝐽 , the energy of the jth state.
ii)The statistical weight of these states , which for the jth state will be 2j+1,
Hence the population in the jth state will be ,
−𝐸𝐽
𝑁𝐽 ∝ (2j + 1)𝑒 𝐾𝑇
ℎ2
Putting 𝐸𝐽 = 𝑗(𝑗 + 1) = 𝐵ℎ𝑐𝑗(𝑗 + 1),
8𝜋2 𝐼
ℎ
𝐵 = , is called rotational constasnt.
8𝜋2 𝐼𝑐
−𝐵ℎ𝑐𝑗(𝑗+1)
𝑁𝐽 ∝ (2j + 1)𝑒 𝐾𝑇

−𝐵ℎ𝑐(2j+1)
𝑑
For the maxima, [(2j + 1)𝑒 𝐾𝑇 ]=0
𝑑𝑗
−𝐵ℎ𝑐𝑗(𝑗+1)
𝐵ℎ𝑐
Or, [(2 − (2j + 1)2 ] 𝑒 𝐾𝑇 =0
𝐾𝑇
2𝐾𝑇
Or, (2j + 1) =√
𝐵ℎ𝑐

𝐾𝑇 1
Or, j=√ −
2𝐵ℎ𝑐 2

Working principle of micro-oven

Cooking with Microwaves
Microwave cooking is a process of exciting the water molecules in food. Food substance that
does not contain water, such as oil, usually does not get cooked by microwaves. Water
molecules are polar molecules with one end dominated by a negative charge and the other by
a positive charge. The typical frequency of the microwave produced by a microwave oven is of
the order of 2.5 X 10 9Hz). That is to say, the electric fields produced by the magnetron
oscillate back and forth at the rate of 2.5 billion times per second (defining 1 billion =
1,000,000,000). Since the water molecules are polarized, the water molecules in the food will
also get pulled back and forth at the rate of about 2.5 billion times per second. This rapid
back-and-forth motion between water molecules creates friction, and hence heat.
In order for microwaves to distribute evenly around the food, a turntable or a rotating source
is often used.

Vibrational spectra :
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 Let’s play physics 9681634157
The rigid rotator model of a di atomic molecule is an idealized model. Actually the two
atoms vibrates along the line of joining while rotating as if they are connected by mass
less spring . ie the displacement is small, the vibration can be regarded as simple
harmonic.
In such approximation, the force acting on a molecule will be 𝐹 = −𝐾𝑥, 𝑥 is relative
the displacement from equilibrium position(𝑥 = 0) of the atoms, K the force constant ,
measures the stiffness of the bond. corresponding to this force, there will be a potential
dV
𝑉(𝑥) such that 𝐹 = −
dx
𝑥
Or 𝑉(𝑥) = − ∫0 𝐹𝑑𝑥 𝑚1 𝑚2
𝑥
𝑉(𝑥) = ∫0 𝐾𝑥𝑑𝑥 𝑥 =0 𝑥
1
𝑉(𝑥) = 𝐾𝑥 2
2

̅𝝂𝟎
wave no. in 𝐜𝐦−𝟏

If we solve Schrödinger wave equation for this potential , which is same as L.H.O.
1
We get the energy Eigen value 𝐸𝑛 = (𝑛 + ) ℎ𝑓0 , 𝑓0 is the oscillation of frequency,
2
1 𝑘 𝑚1 𝑚 2
𝑓0 = √ where the reduce mass 𝜇 = .
2𝜋 𝜇 𝑚1 + 𝑚 2

𝑛 is the vibrational quantum number can have values 0,1,2……

➢ The energy levels are equispaced , with the difference ℎ𝑓0 .
➢ The selection rule of transition between the energy levels ∆ 𝑛 = ±1
Thus under such transition we get spectral line of frequency 𝑓0 , or wave number
1 𝑘
𝜈̅ = 𝜈̅0 (= √ ) Q: why all the molecules do no response in vibrational spectroscopy?
2𝜋𝑐 𝜇

Vibrational rotational spectra :

A di- atomic molecule can vibrate well as rotate when sufficiently excited. It results
Vibrational rotational spectra.
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 Let’s play physics 9681634157
According to Born Oppenheimer approximation, the vibration and rotation of a
molecule can take place independently each other.
Thus we consider the total energy of a molecule is the sum of vibration and rotational
energy.
1 ℎ2
Hence 𝐸𝑛,𝐽 = 𝐸𝑛 + 𝐸𝐽 = (𝑛 + ) ℎ𝑓0 + 𝑗(𝑗 + 1)
2 8𝜋2 𝐼
1
= (𝑛 + ) ℎ𝑓0 + 𝐵ℎ𝑐(𝑗 + 1)
2
Since 𝐸𝜈 ≫ 𝐸𝐽 , the gaps between the consecutive vibrational levels are also large
compare to the gaps between the consecutive rotational levels. So for a given 𝜈, the
rotational quantum number can have different j values.

An analytic expression for the transition can be obtained considering the

selection rule ∆j = ±1,. Considering only the 𝑛 = 0 to𝑛 = 1 transition, where j’ and j’’
are the rotational quantum states for these states we have the expression on term of
the wave number
(𝐸𝑛=1 + 𝐸𝑗=𝑗′ )−(𝐸𝑛=2 + 𝐸=𝑗′′)
𝜈̅𝑗,𝑛 =
ℎ𝑐
1 1
[(1+ )ℎ𝑓0 + 𝐵ℎ𝑐𝑗 ′ (𝑗 ′ +1)]−[(0+ )ℎ𝑓0 + 𝐵ℎ𝑐𝑗 ′′(𝑗 ′′ +1)]
2 2
=
ℎ𝑐
′ ′′ )(𝑗 ′ ′′
=𝜈̅0 + 𝐵(𝑗 − 𝑗 + 𝑗 + 1)

The selection rule for the di atomic molecules for such transitions are
∆𝑗 = ±1 ; ∆𝑛 = ±1, ±2, ±3 … ..
Now we consider the two cases;
i) ∆𝑗 = +1: i.e. 𝑗 ′ − 𝑗 ′′ = 1, 𝑜𝑟 𝑗 ′ = 𝑗 ′′ − 1
Hence 𝜈̅𝑗,𝜈 = 𝜈̅0 + 2𝐵(𝑗 ′′ + 1) where 𝑗 ′′ = 0,1,2,3 … … … .

ii) ∆𝑗 = −1: i.e. 𝑗 ′ − 𝑗 ′′ = −1, 𝑜𝑟 𝑗 ′′ = 𝑗 ′ + 1

Hence 𝜈̅𝑗,𝜈 =𝜈̅0 − 2𝐵(𝑗 ′ + 1) where 𝑗 ′′ = 0,1,2,3 … … ….
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 Let’s play physics 9681634157

The above equations represent the combine rotational and vibrational spectrum. It will
consists of equally spaced lines with spacing 2B , on each side of the band origin 𝜈̅0 . But 𝜈̅0
itself is absent.
The lines to the low frequency side of 𝜈̅0 (∆𝑗 = −1) are called P branch , while those to
the other side (∆𝑗 = 1) are called R branch .

Raman effect : When a beam of monochromatic radiation (or radiation of

very narrow frequency band) is scattered by a transparent media, and the light
scattered at right angles to the incident beam is examined , it is found to contain other
fequencies, above and below that of incident frequency. This form of incoherent
scattering in which the frequency of incident beam under goes a definit change was
observed and studied by Raman in 1928 and is called Raman effect .
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 Let’s play physics 9681634157
The lines on the low frequency side are called stokes line and the higher frequency side
are called anti-sokes lines.

Charecteristics of Raman line:

i) Spectral lines of higher (anti-sokes)and lower frequencies (stokes) were observed.
ii) Both stokes and anti stokes lines are symmetrically situated on either side of the
parent line.
iii) The frequency difference between Raman lines depends on the nature of the
scatterer , indepent of the frequency of the incident radiation.
iv) The stokes lines are more intense thanthe antiskokes line.
v) The intensities of Raman lines are ~1% of that parent lines in solid. For liquid and
gases these are still smaller.
vi) The degree of polarisation for different lines are different .

Quantum theory of Raman effect : Raman effect is due to the interaction between a photon
and a molecule (or atom or ion) of the scatterer . When a photon of frequency 𝜈0 is
scattered by a molecule , its quantum state may or may not be changed.
Let W1 and W2 be the intrinsic energies corresponding to the initial and final state
respectively of the molecule. If 𝜈 ′ be the frequency of the incident photon , then from
conservation of energy ,
1 1
mv2 2 + W2 + h𝜈 ′ = mv1 2 + W1 + h𝜈0
2 2
Where m is the mass of the molecule and v1 , v2 are the velocities before and after
collision. Taking kinetic energy to remain the same ,
W2 + h𝜈 ′ = W1 + h𝜈0
Or, ℎ𝜈 ′ = ℎ𝜈0 + W1 − W2
∆𝑊
Or, 𝜈 ′ = 𝜈0 +
ℎ
Above discussion may arise three cases,
𝐖𝟏 = 𝐖𝟐 ; 𝝂′ = 𝝂𝟎 : Under this condition the photon scatter without causing any
change in quantum state of the molecule. Thus ∆W = 0; 𝜈 ′ = 𝜈0 . Hence
there is no change in frequency, the scattered photons give unmodified lines.

i) 𝐖𝟏 < 𝐖𝟐 ; 𝝂′ < 𝝂𝟎 : Here the collision of the photon with the molecule is such that
the molecule gains some energy from the photon , and the molecule goes from initial
lower( 𝐖𝟏 ) energy state to the final higher energy state (𝐖𝟐 ) . Hence ∆𝑊 is negative.
∆𝑊
Thus 𝜈 ′ = 𝜈0 −
ℎ
The frequency of the scattered photon is higher than that of incident photon.
As a result, stokes lines in Raman spectra occur.
ii) 𝐖𝟏 > 𝐖𝟐 ; 𝝂′ > 𝝂𝟎 : Here the collision of the photon with the molecule in excited
state is such that the photon gains some energy from the molecule , and the molecule

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 Let’s play physics 9681634157
goes from initial higher (𝐖𝟏 )energy state to the lower final energy state (𝐖𝟐 ) . Hence ∆𝑊
is positive.
∆𝑊
Thus 𝜈 ′ = 𝜈0 +
ℎ
The frequency of the scattered photon is less than that of incident photon
resulting anti-stokes lines in Raman spectra occur.

Intensity of Raman spectra : The intensity of a spectral line depends on the transition
probability of the atoms, molecules, taking part collision with photons.
According to the MB statistics , the number of molecules n per unit volume in an
energy state W at temperature T is,
−𝑊
𝑛 = 𝑛0 𝑒 𝐾𝑇 , 𝑛0 is the number of molecule in ground state.
Plainly, number of molecules decreases as the energy level increases.
So at the room temperature , most of the molecules are in the lower energy state, and the
probability from lower state to higher state is greater than the reverse . this explains why
the stokes lines are more intense than the anti -stoke lines.

Note: Raman scattering is different from Rayleigh scattering. It is coherent

scattering which can be considered to be elastic scattering, in which there is no
change of frequency of the scatter photon. The intensity of the scattered radiation
varies inversely to the fourth power of the wavelength.

Rotational structure of Raman spectrum: The Raman lines originates due to the
transition between the vibration or rotational states of the molecules. If the vibrational
state of a molecule remains unchanged due to Raman transition, there will be transition
between the rotational states of the molecules.

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 Let’s play physics 9681634157
Under the influence of the incident photon, the molecule first makes an initial transition
from initial state A(specified by rotational quantum number 𝑗𝑎 ) to some intermediate
virtual state C( jc ) ; then another transition to final energy state B( jb ). There the
selection rule governing the transition will be ∆j=0,±2.
The selection rule for the rotational transition ∆j=±1. Hence the selection rules for
Raman spectra will be ;
i) ∆j= 0; {for( jc − ja ) =±1 and ( jb − jc ) =∓1}
ii) ∆j=± 2; {for( jc − ja ) =±1 and ( jb − jc ) =±1}
An analytic expression for the transition can be obtained considering the selection rule ∆j
= 0,±2,. Considering transition where j’ and j’’ are the rotational quantum states for initial
and the final states .
ℏ2
Now the rotational energy level of a molecule is 𝐸𝐽 = 𝑗(𝑗 + 1) = 𝐵ℎ𝑐𝑗(𝑗 + 1)
2𝐼
ℎ
𝐵 = , is called rotational constant.
8𝜋2 𝐼𝑐
We have the expression in term of the change in wave number∆ (𝜈̅𝑗 ), due to Raman
𝐸𝑗′ − 𝐸𝑗′′
scattering , ∆ 𝜈̅𝑗 =
ℎ𝑐
𝐵ℎ𝑐𝑗 ′ (𝑗 ′ +1)−𝐵ℎ𝑐𝑗 ′′ (𝑗 ′′ +1)
=
ℎ𝑐
′ ′′ )(𝑗 ′
= 𝐵(𝑗 − 𝑗 + 𝑗 ′′ + 1)
The selection rules for such transitions are
∆𝑗 = 0, ±2 ;
Now we consider the three cases;
a) ∆𝑗 = 0: 𝑗 ′ − 𝑗 ′′ = 0, 𝑜𝑟 𝑗 ′ = 𝑗 ′′ ;
Hence ∆ 𝜈̅𝑗 = 0 ,this explains the origin of the unmodified(parent) lines.
b) ∆𝑗 = +2 or, 𝑗 ′ − 𝑗 ′′ = 2, 𝑜𝑟 𝑗 ′ = 𝑗 ′′ + 2
3
Hence ∆ 𝜈̅𝑗 = 2𝐵(2𝑗 ′′ + 3) = 4𝐵 (𝑗 ′′ + ) where 𝑗 ′′ = 0,1,2,3 … … ….
2
These upper frequency sides are anti-stokes lines. Spacing between the parent line and 1st
Raman line in upper frequency side =6B, and between two consecutive lines 4B.
c) ∆𝑗 = −2 or, 𝑗 ′ − 𝑗 ′′ = −2, 𝑜𝑟𝑗 ′′ = 𝑗 ′ + 2
3
Hence ∆ 𝜈̅𝑗 = −2𝐵(2𝑗 ′ + 3) = −4𝐵 (2𝑗 ′ + ) where 𝑗 ′ = 0,1,2,3 … … ….
2
These upper frequency sides are stokes lines. Spacing between the parent line and 1st
Raman line in upper frequency side =6B, and between two consecutive lines 4B.

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 Let’s play physics 9681634157

Region of the Main interactions with matter

spectrum

Radio Collective oscillation of charge carriers in bulk material (plasma oscillation). An

example would be the oscillation of the electrons in an antenna.
(3 x 106 - 3 x1010)

Microwave Plasma oscillation, molecular rotation

(3 x 1010 - 3 x1012)

infrared Molecular vibration, plasma oscillation (in metals only)

(3 x 1012 - 3 x1014)

Visible Molecular or atomic electron excitation (including pigment molecules found in

the human retina)
(3 x 1014 - 3 x1016)

Ultraviolet Excitation of molecular and atomic valence electrons, including ejection of the
electrons (photoelectric effect)
(3 x1016)

X-rays Excitation and ejection of core atomic electrons, Compton scattering (for low
atomic numbers)
(3 x 1016 - 3 x1018)

Gamma rays Energetic ejection of core electrons in heavy elements, Compton

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 Let’s play physics 9681634157
(3 x 1018 - 3 x1016) scattering (for all atomic numbers), excitation of atomic nuclei, including
dissociation of nuclei

High-energy gamma Creation of particle-antiparticle pairs. At very high energies a single photon
rays can create a shower of high-energy particles and antiparticles upon interaction
with matter.

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 Let’s play physics 9681634157

2. In the case of hydrogen atom, electrons having the same principle quantum number but
different orbital angular momentum quantum number have the same energy. But for an
alkali atom this does not seem to be the case-explain. How is the term value expression
modified to take this into account? [3+2] [CU 2000]
4. The sodium D1 line is due to the spectroscopic transition. 𝟑𝟐 𝑷𝟏 → 𝟑𝟐 𝑺𝟏 Calculate the g-
𝟐 𝟐
values of these two levels. [4] [CU 2001]
5. Obtain expression for the splitting of the above two levels under the action of a magnetic
field (Zeeman effect) and sketch the allowed transitions between levels mentioning the
selection rules. [2001]
6. Determine the states which can be formed form a two electron configuration in the L-S
coupling scheme, given 𝒍𝟏 = 𝟑 and 𝒍𝟐 = 𝟐.[4][CU 2001]
7. Explain the fine structure observed on the hydrogen spectrum? [3][CU 2002]
8. Why is the Na-D line a doublet? [3] [CU 2002]
9. What is meant by pure rotation spectra and rotation vibration spectra of a diatomic
molecule? [4] [CU 2002]
10. “Raman shift depends on the nature of the substance under investigation and not on the
wavelength of the original line”.- Discuss. [3] [CU 2002]
11. When do you observed normal Zeeman effect? [3] [CU 2002]
12. Obtain a relation between Einstein’s A and B coefficients. Show that (a) For normal
optical source (𝑻~𝟏𝟎𝟑 𝑲, 𝝀 ≈ 𝟔𝟎𝟎𝟎𝑨̇) emission is incoherent. [4+3] [CU 2003]

13. For 𝟐𝑷 → 𝟏𝑺 transition in hydrogen atom, the mean spontaneous life time is
𝟏. 𝟔𝟔 × 𝟏𝟎−𝟖 sec and the frequency of emitted radiation is 𝟐𝟒 × 𝟏𝟎𝟏𝟓 𝑯𝒛. Calculate the
probability of the stimulated emission. [3] [CU 2003]
14. Develop the theory of population inversion. [4] [CU 2003]
15. What is kerr-electro optic effect? [2] [CU 2003]
17. In a stern-Gerlach experiment, a beam of silver atoms with average kinetic energy
𝒅𝑩𝒛
𝟒 × 𝟏𝟎−𝟐𝟎 𝑱 pass the through an inhomogeneous magnetic field 𝟎. 𝟕𝟓 𝒎 long with 𝒂 =
𝒅𝒛
𝟐𝟓𝟎𝟎𝟎 𝒘𝒃/𝒎𝟑 along the path. What will be the separation between the two parts of the
beam when it emerges from the magnetic field? [6] [CU 2004]

35
 Let’s play physics 9681634157
18. In a many electrons atom, the orbital, spin and total angular momentum are denoted by
L, S and J respectively. If L=2, S=1 and J=2. Find the angle between, L and S using the vector
atom model. [4] [CU 2004]
19. what is the electron configuration of the ground state of Sodium atom? What are the L, S,
J quantum numbers of the state? Describe the Zeeman effect for its D lines quantitatively.
[2+2+6] [CU 2005]
20. Describe briefly the theory of Raman effect. Why are the stokes lines brighter than anti-
stokes line? [4+2] [CU 2005]
21. Write down the commutation relations between position and momentum. Define the
orbital angular momentum operator ⃗𝑳. Derive the commutation relation between its
components, show that ⃗𝑳𝟐 commutes with all of them. [2+2+4+2] [CU 2006]
22. Give two corrections to the Hamiltonian of a Hydrogen-like atom. Show how the doublet
structure of the Na-spectrum arises on of them. [5+5] [CU 2006]
23. Explain with a neat diagram why the 𝑵𝒂 − 𝑫𝟐 lines split under a magnetic field. [4] [CU
2007]
24. Calculate the difference in a wavelength between the first members of the Balmer series
of 𝑯𝟏 and 𝑯𝟑 .

25. What is L-S Coupling? Explain with examples. (CU 2008) 2

26. Show that In a pure Rotational Spectrum of a Diatomic gas, the spectral lines are equally
spaced in frequency. [The expression for energy level may be used. (2011, 2008, 2017)
2
27. a) Write down the electronic configuration of the ground sate of Na atom(Z=11)
(2013,2008)
b) Find out the different states I L-S coupling scheme for a two electron atom. Given 𝒍1=3,
𝒍2=1. (2008)

c) In a Stren-Gerlach Experiment with Ag, the following data were obtained. Initial speed
of the silver atom 103m/sec, length of the magnetic field zone 0.3m,rate of variation of flux
density 1.6T/mm, distance of screen from mid-point of magnetic field 0.10m. (2008)
If the magnetic moment along the magnetic field is given by 9×10-24 J/T, Obtain the
maximum separation between the two traces. Deduce the formula you use. (2008)
2+3+5
28. a) What is Moseley’s Law? Explain it from the Bhor model of atom. (2008, 2011)
36
 Let’s play physics 9681634157
b) Discuss the general Quantum Mechanical Theory of Anomalous Zeeman Effect with
Special reference to Zeeman pattern for D1 and D2 lines of sodium. (2008, 2013)
(2+2)+6
29) The ground state of the Cl atom is 2P3/2. Find out the magnetic moment of a Cl atom in its
ground state. (2009, 2012, 2015) 2
30) State Hund’s Rule .Write down the electronic configuration (metioning all the quantum
numbers) of 7N. (2009, 2014, 2016) 2+2
31) In Stren-Gerlache Experiment a beam of atoms is passed through an inhomogeneous
magnetic field , What will happen if ions used instead of atoms? (2009)
2
32)
a) State the origin of Continuous and Characteristic X-ray spectra. (2009)
2+2
b) I an X-ray Tube containing tungsten as metal, a voltage of 50Kv is applied. Calculate
the minimum X-ray wavelength that will be emitted. If the material of the target is
replaced by Mo. Will there be any change in minimum wavelength? Justify your
Answer.(1eV=1.6×10-19J, h=6.63× 10-34J sec ) (2009)
2+1
c) Pure Rotational spectrum is almost always seen as absorption lines, and not as
emission lines. Explain. (2009,2016) 3

33)
a) Enumerate briefly the Theory of Raman Effect. Why are the Stokes lines brighter than
the Anti-Stokes lines?(2009,2014) 4+2
b) Obtain an expression of Lande g Factor in terms of L, S and J. (2013, 2009,
2016) 2
c) Can Li (Z=3) have rise to Normal Zeeman Effect? Justify your Answer. (2009, 2013,
2016) 2
34) Why is Pure Vibration Spectra observed only in liquids? Explain. (2010, 2016)
2
35)
a) In the Stren-Gerlach experiment why is it necessary to use a beam of neutral atoms
and not of ions? What was the aim of the Experiment. If one performs the experiment

37
 Let’s play physics 9681634157
with an atom of total angular momentum J, how many lines will be obtained.(2010,
2013, 2014) 2+1
b) Find the g value for 3S1 and 3P1 energy levels. Draw the schematic diagram of various
allowed transitions between the various levels due to Anamolous Zeeman Splitting.
(2010) 2+3
c) Which of the following substances can give rise to Pure rotational-vibration
spectra? Justify your Answer
H2, HF, O2, CO, C𝑶𝟐 , 𝑵𝟐
(2011, 2015) 2
36)
a) What are the Stokes and Anti-Stokes lines in Raman spectra? (2010, 2017)
3
b) Calculate the angle between the total and orbital angular momentum vectors for the
4D3/2 state. (2010, 2012, 2013)
3
c) The spacing between vibrational level of CO molecule is 0.08 eV. Calculate the value of
force constant of the CO bond. Given that the masses of C and O atom are 2.0×10-26 kg
2.7×10-26 Kg respectively. (ℏ=6.58×10-16eV sec) (2010, 2016)
4
37) What is Lande g factor ? What is the value for a S-electron? (2012)
2
38) H2, N2 and O2 do not show Vibration Spectra. Why? (2012, 2016) 2
39)
a) In a Stren-Gerlach Experiment a beam of silver atoms with velocity v enter an
𝝏𝑩
inhomogeneous magnetic field of gradient 𝝏𝒁
and length𝒍. After entering from the
magnetic field, they travel a distance b before reaching the screen. Calculate the
magnitude of the splitting.(2012)
4
b) Using the vector diagrams determine the possible values of the total angular
momentum of an electron system for which L=3, S=5/2. (2012)
2
c) Which of these elements H, He, Mg, Li and Na exibit only Normal Zeeman Effect and
Why? (2012) 1+1
40)
d) Outline the main features of Raman scattering. (2012) 3
38
 Let’s play physics 9681634157
e) The Quantum Numbers of two electrons in a two-valence electron atom are
n1=6, 𝒍1=3, s1=1/2; n2=5, 𝒍2=1, s2=1/2
i) Assuming LS coupling ,find possible values of L and hence J
ii) Assuming JJ coupling find the possible values of J. (2012,2016)
3
f) Write down the ground state electronic configuration of Copper(Z=29) (2012)
1
41)
a) Establish a realtion between Einstein’s A and B co-efficient and hence comment on
the incoherency observed in ordinary light. (2013,2015)
5
b) The energy levels corresponding to the Pure Rotational Spectrum of Diatomic
molecules is given by Ej = BJ (J+1), where B is a constant. If 𝝀𝟏 and 𝝀𝟐 be the
wavelengths of lines corresponding to transitions J→J+1 and J+1→J+2 respectively,
find B in terms of these wavelengths. (2013,2016)
2
c) Consider a single electron atom with orbital angular momentum L=√ 2ℏ. What are
the possible values of a measurement of the z component of L. (2013)
2
42) Find out the different states I L-S coupling scheme for a two electron atom. Given
𝒍1=2, 𝒍2=1. 2
43) State Pauli’s exclusion principle.(2013) 2
44) Given that the energy of a hydrogen like atom taking into account fine structure
corrections is of the form
𝒁𝟐 𝜶𝟐 𝒏 𝟑
Enl=En[𝟏 + 𝒏𝟐
( 𝟏 − )]
𝟒
𝒍+
𝟐
Where n and l represent the principal and orbital quantum numbers respectively, and
𝟏
𝜶=
𝟏𝟑𝟕
, show that for fixed n the difference between the maximum and minimum
energy as l varies from 0 to n-1 is equal to 𝑬𝒏 𝒁𝟐 𝜶𝟐 𝟒(𝒏 − 𝟏)/𝒏(𝟐𝒏 − 𝟏) (2013)
3
45) Can hydrogen molecules give rise to Pure-Rotation Spectra? Justify your
answer. (2013)
3
46) Consider an atom with electronic configuration 1 𝒔𝟐 𝟐𝒔𝟐 𝟐𝒑𝟏 . Find possible
values of l, s, j. Also find the magnitude of angular momenta L, S ,J.(2013)
3
47) Show that for a hydrogen atom , the degeneracy of an energy level with
principal quantum number n is 𝟐𝒏𝟐 .(2014)
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 Let’s play physics 9681634157
2
48) using the vector atom model, find the possible values of the total angular
momentum for L=3, S=3/2.(2014)
2
49) If one ignores the electron-electron repulsion completely (a very rough
approximation), what will be ground the state energy of the Be atom? What will be
the value of its first ionization potential? (2014)
3+2
50) What is the origin of fine structure for a Hydrogen like atoms? How the Lyman
𝜶 𝒍𝒊𝒏𝒆 is split due to fine structure? (2014)
2+3
51) For normal Zeeman effect in hydrogen, explain how Lorentz triplet occurs.
How are 𝝅 and 𝝈 lines polarized? (2014)
3+2
52) Consider a 4-level system in which lasing transition occurs between the levels
2→ 𝟑. Show that a necessary condition for population inversion is 𝜸𝟏𝟎 > 𝜸𝟐𝟏 where 𝜸
stands for spontaneous decay rate and 0 denotes the ground state. (2014, 2016 )
4
53) Find the angle between the total and orbital angular momentum vectors for an
electron in 4F3/2 state. (2015) 2
54) Write down the electronic configuration of Mg atom. Hence find the term symbol of its
ground state. (2015) 2
55) What is space quantization? Explain with a suitable diagram. How can you verify it from
Stern-Gerlach experiment 6
56) Discuss the Theory of Anomalous Zeeman Effect. (2015) 6
57) Show that Rotation-Vibration bands are in near infrared region but having rotational
character.(2015) 4
58) You have to measure the first line in the rotation spectrum of CO as 3.842𝒄𝒎−𝟏 .
Calculate the moment of inertia of a CO molecule. (2015)
2
59) How many spectral lines appear in the Zeeman splitting of the 2D3/2→2P1/2 transition of
Na. Explain. (2015) 4
60) Write down the spectral symbol of the term with S=1/2, J=5/2 and Lande g factor
=6/7. (2016) 2

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61) In a Stern-Gerlach experiment, a collimated beam of neutral atoms is split up into seven
equally spaced lines. What is the total angular momentum of the atom? (2016)
2
62) Under what condition normal Zeeman effect can be observed? (2017) 2
63) What is the Threshold population inversion? (2017) 2
64) In a Stern-Gerlach Experiment, a beam of silver atoms moving with a velocity of
𝟏𝟎𝟓 cm/sec passes through an inhomogeneous magnetic field of gradient 0.5 𝑾𝒃𝒍𝒎𝟐 /𝒄𝒎
along z axis for a distance of 10 cm . What is the separation between the two components of
He beam as it comes out of the magnetic field? (2017)
4
65) Explain the splitting of atomic spectral lines in presence of a moderate magnetic field
by taking spin into account. Hence, explain the splitting of the (2𝑷𝟑/𝟐 → 𝟏𝑺𝟏/𝟐 ) and
(2𝑷𝟏/𝟐 → 𝟏𝑺𝟏/𝟐 )

Lines of the hydrogen spectrum in a moderate magnetic field. Give a neat diagram. (2017)
3+3
66) What is the role played by an optical resonator in a laser system? (2017)
2
67) For 2P→ 𝟏𝑺 transition in hydrogen atom, the mean spontaneous life0time is
1.66×𝟏𝟎−𝟏𝟖 sec and the frequency of the emitted radiation is 2.4×𝟏𝟎𝟏𝟓 Hz. Calculate the
probability of stimulated emission. (2017) 3

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