Generalized Angular Momenta and Spin

(a) Generalized angular momentum. Electron’s magnetic Moment and Spin Angular Momentum. J = L + S.
Gyromagnetic Ratio and Bohr Magneton and the g factor. Energy associated with a magnetic dipole
placed in magnetic field. Larmor’s Theorem. Stern-Gerlach Experiment.

(b) Addition of angular momenta - statement only. Allowed values of angular momentum.

Angular momentum and magnetic momentum:- Consider an electron of mass

𝑚 and charge 𝑒 rounds the nucleus of an atom in a circular orbit of radius 𝑟 with a
velocity 𝑣⃗. 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

𝐿⃗⃗ = 𝑟⃗ × 𝑚𝑣⃗ = 𝑚𝑣𝑟 𝑛̂ [∴ considering circular orbit)
The ratio of magnetic moment to the angular momentum is known as gyromagnetic ratio
on given as ,
𝜇 𝑒𝑣𝑟 𝑒
=− =− … … … (𝑖𝑖𝑖)
𝐿 2𝑚𝑣𝑟 2𝑚
In vector notation,
𝑒
𝜇⃗ = − 𝐿⃗⃗ … … … … … (iv)
2𝑚

The −𝑣𝑒 𝑠𝑖𝑔𝑛 shows the direction of the magnetic moment is opposite to that of orbital
angular momentum.
According to Bohr’s theory, the angular momentum of the electron is quantized in the unit
of ℏ and given by.
 𝐿 = √𝑙(𝑙 + 1) ℏ
From equation (3) ignoring the sign,
𝑒
𝜇𝑙 = √𝑙(𝑙 + 1)ℏ
2𝑚
𝑒ℏ
= √𝑙(𝑙 + 1)
2𝑚
= 𝜇𝐵 √𝑙(𝑙 + 1)
𝑒ℏ
Where 𝜇𝐵 = = 9.274 × 10−24 𝐽𝑜𝑢𝑙𝑒/𝑡𝑒𝑠𝑙𝑎
2𝑚

This is known as Bohr magneton, the basic unit of atomic magnetic moment.

Q: Calculate the angular momentum and magnetic moment for 𝑙 = 2.

Interaction with magnetic field:

Toque and Larmor precession

When an external magnetic field 𝐵 ⃗⃗ is applied, it interacts with the orbital magnetic
moment 𝜇⃗ and a torque acts as,
𝑒 𝑒
⃗⃗ = −
𝜏⃗ = 𝜇⃗ × 𝐵 𝐿⃗⃗ × 𝐵⃗⃗ = ⃗⃗ × 𝐿⃗⃗
𝐵
2𝑚 2𝑚
𝐿⃗⃗ = corresponding angular momentum.
⃗⃗⃗⃗⃗
𝑑𝑙
How ever 𝜏⃗ = ;
𝑑𝑡

𝑑𝐿⃗⃗ 𝑒
∴ = ⃗⃗ × 𝐿⃗⃗
𝐵
𝑑𝑡 2𝑚
This is the expression of Gyroscopic motion, clearly 𝐿⃗⃗ precesses
𝑒
with angular velocity 𝜔
⃗⃗ = ⃗⃗
𝐵
2𝑚
𝜔 𝑒𝑩
Therefore 𝑓 = = is known as precessional frequency.
2𝜋 4𝜋𝑚
Q: Calculate the precssional freqequency when the orbital with 𝑙 = 2 is placed under
magnetic field of strength 1T.

Interaction energy
Let an atom having orbital angular momentum 𝐿⃗⃗ only, be placed in an external magnetic
⃗⃗ = 𝐵𝑧̂ .
field 𝐵
The interaction energy ∆∈ of the atom due to interaction between magnetic field and
magnetic moment 𝜇⃗𝑙 ,
⃗⃗
∆∈ = −𝜇⃗𝑙 ∙ 𝐵

Now magnetic moment in term of angular momentum 𝐿⃗⃗, ,

𝑒
𝜇𝑙 = − 𝐿⃗⃗
2𝑚
∆∈ = −𝜇⃗𝑙 ∙ 𝐵 ⃗⃗
𝑒
= 𝐵𝐿⃗⃗ ∙ 𝑧̂
2𝑚
𝑒
= 𝐵𝐿
2𝑚 𝑍
𝑒
= 𝐵𝑚𝑙 ℏ
2𝑚
𝑒ℏ
= 𝑚𝑙 ( )𝐵
2𝑚
= 𝑚𝑙 𝜇𝐵 𝐵
The total energy of the electronic state 𝐸𝑛𝑙𝑚 = 𝐸𝑛𝑙 + 𝑚𝑙 𝜇𝐵 𝐵
𝐸𝑛𝑙 is the energy of the state before applied field.
Since 𝑚𝑙 can have (2𝑙 + 1) values from to 𝑙 𝑡𝑜 − 𝑙[𝑙, (𝑙 − 1) … .0 … . −(𝑙 − 1), −𝑙] the energy
can have (2𝑙 + 1) each slightly differ by 𝜇𝐵 𝐵.
In other word the state 𝐸𝑛𝑙 splits in (2𝑙 + 1) number of substates.
Q: Let us consider the states with (𝑙=3);Now the magnetic field 𝐵 ⃗⃗ of applied along 𝑍−𝑎𝑥𝑖𝑠.
i)Draw the different orientations of the atomic plane about Z-axis mentioning the angle made
by the normal of the plane with z axis.
ii) Calculate potential energy of the each of the states (with different 𝑚 𝑣𝑎𝑙𝑢𝑒𝑠.)
iii) Represent this by a simple energy splitting diagram and estimate the splitting of the states
(energy gap between two states.)

Idea of space quantization: -The orbital plane of electron and hence the orbital angular
momentum 𝐿⃗⃗ 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 𝐿⃗⃗ on the direction of applied field,
𝐿 𝑐𝑜𝑠 𝜃 = 𝑚𝑙 ℏ
𝜃 is the angle between 𝐿⃗⃗ and the direction of the applied field and 𝑚𝑙 = 0, ±1, ±2, … .. are
known as magnetic quantum number.

SpaceQuantizationOf
AngularMomentum (2).cdf

AdditionOfAngularMomentaInQuantumMechanics.cdf

Spin angular momentum and magnetic moment :- Due to the spinning

motion of the electron it shows an intrinsic spin angular momentum 𝑆⃗ and spin magnetic
moment 𝜇𝑠
However, the ratio of 𝜇𝑠 to 𝑆 is different from the gyromagnetic ratio for orbital motion
and is given by,
𝜇𝑠 𝑒
= 𝑔𝑠
𝑆 2𝑚
𝑔𝑠 is known as lande- g- factor and here 𝑔𝑠 = 2 (for electron)
𝑒
∴ 𝜇𝑠 = 2. 𝑆
2𝑚
𝑒 𝑒 √3
= 2. √𝑠(𝑠 + 1)ℏ = ℏ = 𝜇𝐵 √3
2𝑚 𝑚 2
So, spin magnetic moment of the electron is equal to √3 Bohr magneton.

The interaction energy due to interaction between magnetic field and magnetic moment
𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛,

∆∈ = −𝜇⃗𝑙 ∙ 𝑆⃗

Now magnetic moment in term of angular momentum 𝐿⃗⃗, ,

𝑒
𝜇⃗𝑠 = − 𝑆⃗
𝑚
⃗⃗
∆∈ = −𝜇⃗𝑠 ∙ 𝐵
𝑒
= 𝐵𝑆⃗ ∙ 𝑧̂
𝑚
𝑒
= 𝐵𝑆𝑍
𝑚
𝑒
= 𝐵𝑚𝑆 ℏ
𝑚
Now according to space quantization, the spinning electrons may orient either parallel or
1
anti parallel to the direction of applied magnetic field assigned as 𝑚𝑧 = ±
2

1 𝑒ℏ
= ± ( )𝐵
2 𝑚
= ± 𝜇𝐵 𝐵

AdditionOfAngularMomentaInQuantumMechanics.cdf
Stern Garlach 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 Garlach 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 = −𝜇⃗𝑠 ∙ 𝐵
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 𝑣 is
𝑙 1 𝜇𝐵 𝑑𝐵 𝑙 2 𝜇 𝑑𝐵
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
Q: a) In Stren-Gerlache Experiment a beam of atoms is passed through an inhomogeneous
magnetic field, What will happen if ions used instead of atoms?

b) If one performs the experiment with an atom of total angular momentum J, how many
lines will be obtained. ((2009, 2010, 2013, 2014) 2+1+1

c) What was the aim of the Experiment.

a) If instead of neutral atom ions which have a charge are used, then moving charged
ions will directly interact with whole Magnetic field where as the information as part of
the field will only interact with the intrinsic dipole moment of the atom. The first effect
will be much greater than the second effect. It will therefore not be possible draw any
direct logical conclusion.
b) Due to space quantization there will be 2𝑗 + 1 number of lines.
c) The Stern–Gerlach experiment demonstrated that the spatial orientation of angular
momentum is quantized. It demonstrated that atomic-scale systems have intrinsically
quantum properties.

Q: In a stern-Gerlach experiment, a beam of silver atoms with average kinetic energy

𝒅𝑩
𝟒 × 𝟏𝟎−𝟐𝟎 𝑱 pass the through an inhomogeneous magnetic field 𝟎. 𝟕𝟓 𝒎 long with 𝒛 =
𝒅𝒛
𝒘𝒃
𝟐𝟓𝟎𝟎
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]
Displacement d along z-direction on emerging from fields will given by,
1 𝜇𝐵 𝑑𝐵𝑧 𝑙𝑚 2 1 𝑑𝐵𝑧 𝑙𝑚 2
1 𝑑𝐵𝑧 𝑙𝑚 2
𝑑=± ( ) = ± 𝜇𝐵 = ± 𝜇𝐵
2 𝑚 𝑑𝑧 𝑣 4 𝑑𝑧 1 𝑚𝑣 2 4 𝑑𝑧 𝐸𝑘
2
𝑤ℎ𝑒𝑟𝑒, 𝑙𝑚 = 𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑎𝑔𝑛𝑒𝑡 = 0.75 𝑚
𝜇𝐵 = 9 × 10−24 𝐽⁄𝑤𝑏⁄𝑚2
𝐸𝑘 = 4 × 10−20 𝐽
𝑑𝐵𝑧 𝑤𝑏
= 2500 3
𝑑𝑧 𝑚
 1 −24
(0.75)2
𝑑 = ± × 9 × 10 × 2500 × = 0.079 𝑚.
4 4 × 10−20
Hence net separation 2𝑑 = 0.158 𝑚.

Q: In Stern-Gerlach Experiment with Ag, the following data were obtained. Initial speed of
the silver atom 103m/sec, length of the magnetic field zone 0.03m, rate of variation of flux
density 1.6T/mm, distance of screen from mid-point of magnetic field 0.10m. 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.
(CU 2008)
Displacement d along z-direction on emerging from fields will given by,
1 𝜇𝐵 𝑑𝐵 𝑙𝑚 2
𝑑=± ( )
2 𝑚 𝑑𝑧 𝑣
𝑤ℎ𝑒𝑟𝑒, 𝑙𝑚 = 𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑎𝑔𝑛𝑒𝑡 = 0.03 𝑚
𝜇𝐵 = 9 × 10−24 𝐽⁄𝑤𝑏⁄𝑚2
𝑣 = 103 𝑚⁄𝑠𝑒𝑐
𝑚 = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑜𝑛𝑒 𝑎𝑡𝑜𝑚 𝑜𝑓 𝑠𝑖𝑙𝑣𝑒𝑟
= 108 × 1.66 × 10−27 𝑘𝑔
𝑑𝐵
= 1.60 × 103 𝑇⁄𝑚
𝑑𝑧
𝑑𝑖𝑠𝑡𝑎𝑐𝑒
1 9 × 10−24 3
0.03 2
𝑆𝑜, 𝑑 = × 1.60 × 10 × ( 3 )
2 108 × 1.66 × 10−27 10
−5
= 3.61 × 10 𝑚
∴ The separation between the two components of the beam as it outcomes of the magnetic
field = 2.510 × 10−6 𝑚

𝐷 𝑂𝐶
From the geometry =
𝑑 𝑎

Here distance of screen from mid-point of

magnetic field (OC)= 0.10m
𝑙𝑚
𝑎 = ℎ𝑎𝑙𝑓 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑎𝑔𝑛𝑒𝑡𝑖𝑐 𝑝𝑎𝑡ℎ 𝑙𝑒𝑛𝑔𝑡ℎ = = 0.015 𝑚
2
𝑂𝐶 0.1×3.61×10−5
Hence 𝐷 = 𝑑= = 2.10 × 10−4 𝑚.
𝑎 0.015

Hence maximum separation on the screen is 2𝐷 = 2 × 2.10 × 10−4 = 4.2 × 10−4 𝑚𝑒𝑡𝑒𝑟.
Q: 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?
[2](2016)
Here 2𝑗 + 1 = 7
∴𝑗=3

Hence total angular momentum, 𝑗⃗ = √𝑗(𝑗 + 1) ℏ = √12 ℏ.

Q: In a Stern-Gerlach Experiment, a beam of silver atoms moving with a velocity of
𝑾𝒃/𝒎𝟐
𝟏𝟎𝟓 cm/sec passes through an inhomogeneous magnetic field of gradient 0.5 along z
𝒄𝒎
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)

Displacement d along z-direction on emerging from fields will given by,

1 𝜇𝐵 𝑑𝐵 𝑙𝑚 2
𝑑=± ( )
2 𝑚 𝑑𝑧 𝑣
𝑤ℎ𝑒𝑟𝑒, 𝑙𝑚 = 𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑎𝑔𝑛𝑒𝑡 = 0.1 𝑚
𝜇𝐵 = 9 × 10−24 𝐽⁄𝑤𝑏⁄𝑚2
𝑣 = 105 𝑐𝑚⁄𝑠𝑒𝑐 = 103 𝑚⁄𝑠𝑒𝑐
𝑚 = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑜𝑛𝑒 𝑎𝑡𝑜𝑚 𝑜𝑓 𝑠𝑖𝑙𝑣𝑒𝑟
= 108 × 1.66 × 10−27 𝑘𝑔
𝑑𝐵
= 10 × (0.5) 𝑤𝑏⁄𝑚3
𝑑𝑧
1 9 × 10−24 0.1 2
𝑆𝑜, 𝑑 = × 5 × ( 3)
2 108 × 1.66 × 10−27 10
= 1.255 × 10−6 𝑚
∴ The separation between the two components of the beam as it outcomes of the magnetic
field = 2.510 × 10−6 𝑚

Q: From the result of Stern -Garlach experiment using the idea of spinning electron
develop Pauli’s spin matrices

Pauli’s Spin Matrices:-

Let 𝑆⃗ define spin angular momentum.
𝑆 2 = 𝑆𝑥2 + 𝑆𝑦2 + 𝑆𝑧2
following the relations,
[𝑆⃗𝑥 , 𝑆⃗𝑦 ] = 𝑖ℏ𝑆𝑧
[𝑆⃗𝑦 , 𝑆⃗𝑧 ] = 𝑖ℏ𝑆𝑥
 [𝑆⃗𝑧 , 𝑆⃗𝑥 ] = 𝑖ℏ𝑆𝑦
[𝑆⃗2 , 𝑆⃗𝑥 ] = [𝑆⃗2 , 𝑆⃗𝑦 ] = [𝑆⃗2 , 𝑆⃗𝑧 ] = 0
1
Stern Gerlach experimental gave 𝑆𝑧 can have only two values ± ℏ. [It is here for 𝑆𝑥 , 𝑆𝑦
2
also]
We define operator 𝜎⃗(matrix) with components 𝜎𝑥 , 𝜎𝑦 , 𝜎𝑧 such that
ℏ ℏ ℏ
𝑆𝑥 = 𝜎𝑥 ; 𝑆𝑦 = 𝜎𝑦 ; 𝑆𝑧 = 𝜎𝑧
2 2 2
These matrices must follow,
(𝑖) 𝜎𝑥2 = 𝜎𝑦2 = 𝜎𝑧2 = 1 as 𝜎𝑥 , 𝜎𝑦 , 𝜎𝑧 must have eigen values at ±1
(𝑖𝑖)Since [𝑆𝑥 , 𝑆𝑦 ] = 𝑖ℏ𝑆𝑧
[𝜎𝑥 , 𝜎𝑦 ] = 2𝑖𝜎𝑧 and so on. [Prove it]
(𝑖𝑖𝑖) 𝜎𝑥 𝜎𝑦 = 𝑖 𝜎𝑧 and so on. [Prove it]
Let us now assign 𝜎𝑧 matrix with eigen value +1, −1 as,
1 0
𝜎𝑧 = ( )
0 −1
To satisfy (𝑖), (𝑖𝑖), (𝑖𝑖𝑖) conditions, it can be shown at
0 1
𝜎𝑥 = ( )
1 0
0 −𝑖
𝜎𝑦 = ( )
𝑖 0
Eigen vectors of 𝜎𝑥 , 𝜎𝑦 , 𝜎𝑧 and Spinors:-
Q: Find the eigen vectors (spinors ) of 𝝈𝒛
𝜓
For +𝟏; let |𝛼 >= ( 1 ) be the eigen vector.
𝜓2
1−1 0 𝜓
𝑜𝑟, ( ) ( 1) = 0
0 −1 − 1 𝜓2
∴ 2𝜓2 = 0 ∴ 𝜓2 = 0
𝜓1 = 𝑎𝑟𝑏𝑖𝑡𝑎𝑟𝑦 = 1(𝑆𝑎𝑦)
1
∴ |𝛼 >= ( )
0
0
Similarly, for −1; it can be shown eigen vector |𝛽 >= ( )
1
Clearly,
ℏ 1 0 1 ℏ 1 ℏ
𝑆𝑧 |𝛼 >= ( ) ( ) = ( ) = |𝛼 >
2 0 −1 0 2 0 2
&
ℏ 1 0 0 ℏ 0 ℏ
𝑆𝑧 |𝛽 >= ( ) ( ) = − ( ) = − |𝛽 >
2 0 −1 1 2 1 2
ℏ ℏ
∴ |𝛼 >, |𝛽 > are the eigen vectors of 𝑆𝑧 for the eigen values , −
2 2

𝑵𝒐𝒕𝒆: −(𝑯. 𝑾. )
 Q: Prove that
𝜎𝑥 |𝛼 >= |𝛽 >;
𝜎𝑥 |𝛽 >= |𝛼 >
𝜎𝑦 |𝛼 > = 𝑖𝛽;
𝜎𝑦 |𝛽 > = −𝑖𝛼
𝜎𝑧 |𝛼 >= 𝛼,
𝜎𝑧 𝛽 >= −𝛽
1.
3 2 1 3
𝑆 2 |𝛼 >= ℏ ( ) = ℏ2 |𝛼 >
4 0 4
3 0 3
𝑆 2 |𝛽 > = ℏ2 ( ) = ℏ2 |𝛽 >
4 1 4
Q: Write down Pauli’s spin matrices 𝝈𝒙 , 𝝈𝒚 𝒂𝒏𝒅 𝝈𝒛 . The eigen vector of the operator
|𝜶>+|𝜷> |𝜶>−|𝜷>
𝝈𝒛 𝒂𝒏𝒅 |𝜶 > 𝒂𝒏𝒅 |𝜷 >. Show that 𝒂𝒏𝒅 are the normalized eigen vectors
√𝟐 √𝟐
of 𝝈𝒙 .
𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛: − We know the Pauli’s spin matrices are,
0 1 0 −𝑖 1 0
𝜎𝑥 = ( ) , 𝜎𝑦 = ( ) , 𝜎𝑧 = ( )
1 0 𝑖 0 0 −1
Now, 𝜓 operator on 𝜎𝑧
𝜓 𝜓
∴ 𝜎𝑧 𝜓 = 𝜎𝑧 ( 1 ) = 𝜆 ( 1 ) [𝜆 = 𝑒𝑖𝑔𝑒𝑛 𝑣𝑎𝑙𝑢𝑒]
𝜓2 𝜓2
1 0 𝜓 𝜓
∴ ( ) ( 1) = 𝜆 ( 1)
0 −1 𝜓2 𝜓2
∴ 𝜆𝜓1 = 𝜓1 ; 𝜆𝜓2 = −𝜓2
∴ 𝜆 = ±1
For the eigen values, 𝜆 = 1
1−1 0 𝜓
( ) ( 1) = 0
0 −1 − 1 𝜓2
0
𝑜𝑟, −2𝜓2 = 0 ⟹ 𝜓2 = 0; 𝜓 = ( )
1
So, 𝜓1 must be arbitrary.
If
1
𝜆=1⟹( )=𝛼
0
0
Putting 𝜆 = −1 ⟹ ( ) = 𝛽
1
0 1 1 0
∴ 𝜎𝑥 𝛼 = ( )( ) = ( ) = 𝛽
1 0 0 1
0 1 0 1
𝜎𝑥 𝛽 = ( )( ) = ( ) = 𝛼
1 0 1 0
𝛼+𝛽 𝛼+𝛽
∴ 𝜎𝑥 ( ) = 𝜆.
√2 √2
 𝛼−𝛽 𝛼−𝛽
𝜎𝑥 ( ) = (−1). ( )
√2 √2
Q: Calculate 𝝈𝒙 𝝈𝒚 𝝈𝒛
0 1 0 −𝑖 1 0
𝜎𝑥 𝜎𝑦 𝜎𝑧 = ( )( )( )
1 0 𝑖 0 0 −1
𝑖 0 1 0
=( )( )
0 −𝑖 0 −1
1 0 1 0
= 𝑖( )( )
0 −1 0 −1
= 𝑖𝐼
[𝑎𝑙𝑡: 𝜎𝑥 𝜎𝑦 𝜎𝑧 = 𝑖𝜎𝑧 𝜎𝑧 = 𝑖𝐼]

⃗⃗⃗, 𝑩
2.The components of 𝑨 ⃗⃗⃗ commute with 𝝈. Show that
⃗⃗⃗)(𝝈
⃗⃗. 𝑨
(𝝈 ⃗⃗⃗) = 𝑨
⃗⃗. 𝑩 ⃗⃗⃗. 𝑩
⃗⃗⃗ + 𝒊 𝝈 ⃗⃗⃗ × 𝑩
⃗⃗. (𝑨 ⃗⃗⃗)
We have,
(𝜎⃗. 𝐴⃗). (𝜎⃗. 𝐵
⃗⃗) = (𝜎𝑥 𝐴𝑥 + 𝜎𝑦 𝐴𝑦 + 𝜎𝑧 𝐴𝑧 )(𝜎𝑥 𝐵𝑥 + 𝜎𝑦 𝐵𝑦 + 𝜎𝑧 𝐵𝑧 )
= 𝜎𝑥2 𝐴𝑥 𝐵𝑥 + 𝜎𝑦2 𝐴𝑦 𝐵𝑦 + 𝜎𝑧2 𝐴𝑧 𝐵𝑧 + 𝜎𝑥 𝜎𝑦 𝐴𝑥 𝐵𝑦 + 𝜎𝑦 𝜎𝑧 𝐴𝑦 𝐵𝑥 + 𝜎𝑥 𝜎𝑧 𝐴𝑥 𝐵𝑧 + 𝜎𝑦 𝜎𝑧 𝐴𝑦 𝐵𝑧
+ 𝜎𝑧 𝜎𝑦 𝐴𝑧 𝐵𝑦 + 𝜎𝑧 𝜎𝑥 𝐴𝑧 𝐵𝑥
= 𝐴⃗. 𝐵⃗⃗ + 𝑖𝜎𝑧 (𝐴𝑥 𝐵𝑦 − 𝐴𝑦 𝐵𝑥 ) + 𝑖𝜎𝑦 (𝐴𝑧 𝐵𝑥 − 𝐴𝑥 𝐵𝑧 )𝑖𝜎𝑥 (𝐴𝑦 𝐵𝑧 − 𝐴𝑧 𝐵𝑦 )
= 𝐴⃗. 𝐵
⃗⃗ + 𝑖𝜎𝑧 (𝐴⃗ × 𝐵
⃗⃗) + 𝑖𝜎𝑦 (𝐴⃗ × 𝐵
𝑧
⃗⃗) + 𝑖𝜎𝑥 (𝐴⃗ × 𝐵
𝑦
⃗⃗)
𝑥
= 𝐴⃗. 𝐵
⃗⃗ + 𝑖𝜎. (𝐴⃗ × 𝐵
⃗⃗)
Note that for 𝐴⃗ = 𝐵⃗⃗,
(𝜎⃗. 𝐴⃗) = 𝐴2 + 𝑖 𝜎⃗. (𝐴⃗ × 𝐴⃗)
= 𝐴2

Q:What is L-S Coupling? Explain with examples. (CU 2008)

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
(i) L-S or Russel-Sauder’s 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 𝐿⃗⃗ . Independently all
their spin angular momenta vectors combine to form a resultant 𝑆⃗ .These resultant 𝐿⃗⃗ and
𝑆⃗ then combine to form the total angular momentum 𝐽⃗ of the atom .
The scheme can be summarised as,

𝐿⃗⃗ = 𝑙⃗1` ⨁ 𝑙⃗2 ⨁ 𝑙⃗3 +∙∙∙∙∙∙= ∑ 𝑙⃗𝑖

𝑆⃗ = 𝑠⃗1` ⨁ 𝑠⃗2 ⨁ 𝑠⃗3 +∙∙∙∙∙∙= ∑ 𝑠⃗𝑖

𝐽⃗ = 𝐿⃗⃗⨁𝑆⃗
If 𝐿𝑖 and 𝑆𝑖 be orbital and spin quantum number of individual
electron then

𝐿⃗⃗𝑖 = √𝑙𝑖 (𝑙𝑖 + 1)ℏ

𝑆⃗𝑖 = √𝑠𝑖 (𝑠𝑖 + 1)ℏ

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

𝐿⃗⃗ = √𝐿(𝐿 + 1)ℏ

𝑆⃗ = √𝑆(𝑆 + 1)ℏ
For 2 electron systems
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; 𝐽⃗ = √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]

Q: Find out the different states L-S coupling of a 𝟑𝒑 electron with a 𝟒𝒅 electron
OR
Find out the different states L-S coupling scheme for a two-electron atom. Given 𝒍1=1,
𝒍2=2. CU (2008,09,)
OR
Find out the different states I L-S coupling scheme for a two-electron atom. Given 𝒍1=2,
𝒍2=1. CU 2013

➢ 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

∴ 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

3 4, 3 , 2 3
𝐹4 , 3𝐹3 , 3𝐹2

1 2 3, 2 , 1 3
𝐷3 , 3𝐷2 , 3𝐷1

1 2, 1, 0 3
𝑃2 , 3𝑃1 , 3𝑃0
1
3 3 𝐹3
1
2 2 𝐷2
0
1
1 1 𝑃1
Q: Find out the different states L-S coupling of a 𝟑𝒑 electron with a 𝟒𝒅 electron
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 𝐽⃗𝑖 = 𝑙⃗𝑖 + 𝑠⃗𝑖 ; The vector sum of all the individual ⃗𝑗⃗𝑖 vectors gives the
total angular momentum 𝐽⃗ of the atom. Thus, ⃗⃗𝑗 = ∑ ⃗𝑗⃗𝑖
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 𝑠2 = ∴ 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
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

Q: In an atom, two electrons have an orbital angular momentum 𝒍𝟏 = 𝟐 and 𝒍𝟐 = 𝟑. What

are the possible values of L, the total orbital angular momentum, S, the total intrinsic spin
and J, the total angular momentum? [3+1] [CU 2000]
Or
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]

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

here 𝑙1 = 2 𝑎𝑛𝑑 𝑙2 = 3
1 1
𝑆1 = 𝑎𝑛𝑑 𝑆2 =
2 2

∴ Possible values of 𝐿 = 5,4,3,2,1,

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 Type equation here.

3
5 6, 5, 4 𝐻6 , 3𝐻5 , 3𝐻4
1 4 5, 4, 3 3
𝐺5 , 3𝐺4 , 3𝐺3
3
3 4, 3 ,2 𝐹4 , 3𝐹3 , 3𝐹2
3
2 3, 2 , 1 𝐷3 , 3𝐷2 , 3𝐷1
3
1 2, 1, 0 𝑃2 , 3𝑃1 , 3𝑃0
1
5 5 𝐻5
0 4 4 1
𝐺4
1
3 3 𝐹3
1
2 2 𝐷2
1
1 1 𝑃1

Q: 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. CU (2012,2016)
Here the given electrons are non-eqivalent.
 𝑙1 = 3 𝑎𝑛𝑑 𝑙2 = 1

1 1
𝑆1 = 𝑎𝑛𝑑 𝑆2 =
2 2

∴ Possible values of 𝐿 = 4,3,2

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

4 5, 4 , 3 3
𝐺5 , 3𝐺4 , 3𝐺3

1 3 4, 3 , 2 3
𝐹4 , 3𝐹3 , 3𝐹2

2 3, 2, 1 3
𝐷3 , 3𝐷2 , 3𝐷1
1
4 4 𝐺4
1
3 3 𝐹3
0
1
2 2 𝐷2

let us consider the J-J coupling

1 7 5
𝑙1 = 3 𝑠1 = ∴ 𝑗1 = ,
2 2 2
1 3 1
𝑙2 = 1 𝑠2 = ∴ 𝑗2 = ,
2 2 2
The four J-J combination gives the following J values
7 3
𝐽1 = , 𝐽2 = 𝐽 = 5,4,3,2
2 2
7 1
𝐽1 = , 𝐽2 = 𝐽 = 4, 3
2 2
 5 3
𝐽1 = , 𝐽2 = 𝐽 = 4,3,2, 1
2 2
5 1
𝐽1 = , 𝐽2 = 𝐽 = 3,2
2 2
The four states are written as,
7 3 7 1 5 3 5 1
( , ) ( , ) ( , ) ( , )
2 2 5,4,3,2 2 2 4,3 2 2 4,3,2,1 2 2 3,2

Q: Atoms with two or more equivalent electrons,

LS coupling of 2p electrons of same principal quantum number 𝒏:

For two equivalent electrons (𝑛, 𝑙 𝑠𝑎𝑚𝑒); remaining quantum numbers 𝑙, 𝑠 must differ.
1 1
For p electrons 𝑙1 = 1; 𝑙2 = 1; 𝑠1 = ; 𝑠2 =
2 2

Thus 𝐿 = 2,1,0; 𝑆 = 1,0

Using Breit’s scheme we can determine all possible values of 𝑀𝐿

corresponds to 𝑀𝐿 = 2(𝐷); 1(𝑃); 0(𝑆) values.

1
When 𝑆 = 1(𝑡𝑟𝑖𝑝𝑙𝑒𝑡); 𝑠1 = 𝑠2 = ; hence they must differ by 𝑚𝑙
2
3
values;(𝑑𝑖𝑎𝑔𝑜𝑛𝑎𝑙 𝑒𝑙𝑒𝑚𝑒𝑛𝑡𝑠 𝑖𝑔𝑛𝑜𝑟𝑒𝑑)Hence only possible states are 𝑃2 , 3𝑃1 , 3𝑃0
 1 1
Again When 𝑆 = 0(𝑠𝑖𝑛𝑔𝑙𝑒𝑡); 𝑠1 = ; 𝑠2 = − ;hence they need not differ by 𝑚𝑙 values;
2 2
Hence possible combinations are 𝑀𝐿 = 2(𝐷); 0(𝑆) as 1(𝑃) excluded as already taken.
Possible states are 1𝐷2 , 1𝑆0

Similarly for 𝑛𝑑 2 state the possible states are;

3
𝑃0,1,2 , 3𝐹1,2,3 , 1𝐺4 , 1𝐷2 , 1𝑆0
(a) Identical particles. Symmetric & Antisymmetric Wave Functions. Pauli’s Exclusion Principle. Hund’s
Rule. Periodic table.
Q: State and explain the rules governing the electronic configuration .
OR
State Pauli’s exclusion principle. 2 (2013)
State Aufbau principle.
State Hund’s law.

Pauli’s exclusion principle : It is impossible for two electrons of a poly-electron atom to

have the same values of the four quantum numbers: 𝑛, the principal quantum number, 𝑙,
the angular momentum quantum number, 𝑚𝑙 , the magnetic quantum number 𝑚𝑙 , and 𝑚𝑠 ,
the spin quantum number.
For example, if two electrons reside in the same orbital, and if their 𝑛, 𝑙, 𝑎𝑛𝑑 𝑚𝑙 values are
the same, then their 𝑚𝑠 must be different, and thus the electrons must have opposite half-
1 1
integer spin projections of and− .
2 2

Aufbau principle: The available energy levels in an atom are filled in the increasing order
of sub-shell energy. The orbital with lower energy is filled first irrespective of shell to
which it belongs.
The sub-shells in an atom are filled in the following order,
1𝑠, 2𝑠, 2𝑝, 3𝑠, 3𝑝, 4𝑠, 3𝑑, 4𝑝, 5𝑠, 4𝑑, 5𝑝, ….

Hund’s rule: According to this rule, electron pairing shall not take place until all vacant
subshell have at least one electron.
Illustration
This rule can be extended as follows
i) The electrons spins are added to get the maximum possible S, as permitted by
Pauli’s principle.
ii) The orbital momenta are combined to get maximum value of L that is consisted
with S as determined in (i).
iii) For partially filled – shell,
𝐽 = 𝐿 − 𝑆 for a shell less than 1/2 filled
= 𝐿 + 𝑆 for a shell more than 1/2 filled
=0 for ½ filled shell.

The filling of different energy levels occurs in such a way that the resulting
configuration has a minimum energy.

For atoms with a large number of electrons, the states or shells are filled according to,
2 10 18 36 54 86
1𝑠 2 2𝑠 2𝑝6
2
3𝑠 3𝑝 4𝑠 3𝑑 4𝑝 5𝑠 4𝑑 5𝑝 6𝑠 4𝑓 5𝑑10 6𝑝6 …..
2 6 2 10 6 2 10 6 2 14

𝐻𝑒 𝑁𝑒 𝐴𝑟 𝐾𝑟 𝑋𝑒 𝑅𝑛

Consult classnote:

Q:What is the electron configuration of the ground state of Sodium atom? What are the
𝑳, 𝑺, 𝑱 quantum numbers of the state?
Or
Write down the electronic configuration of the ground sate of Na atom(Z=11)
(2013,2008)

Ans.
Sodium has atomic number 11.
Hence in ground state the electronic configuration of sodium,
1𝑆 2 2𝑆 2 2𝑃6 3𝑆1
i.e. The first shell 𝑘(𝑛 = 1) filled by two electrons in subshell S(l=0).
The 2nd shell 𝐿 (𝑛 = 2)filled by total 8-electrons with 2 electrons in subshell 𝑆(𝑙 = 0) and
6 electrons in subshell 𝑃(𝑙 = 1). The remaining 1 electron takes the position in subshell
(𝑙 = 0 ) of M.
The atom is characterized by the outer most electron at 3𝑆 1 .
For this electron,
1 √3
𝑠 = ; 𝑆⃗ = √𝑠(𝑠 + 1) ℏ = ℏ
2 4

𝑝 = 1; 𝑃⃗⃗ = √1(1 + 1) ℏ = √2 ℏ
3 1
𝑗 = 𝑙 ⊕ 𝑠; = ;
2 2
Hence,

3 3 √15
𝑗⃗ = √ ( + 1) ℏ = ℏ
2 2 2

1 1 √3
= √ ( + 1) ℏ = ℏ
2 2 2

Q: State Hund’s Rule . Write down the electronic configuration (mentioning all the
quantum numbers) of 7N. (2009, 2014, 2016) 2+2
See previous question.
In ground state the electronic configuration of N- atom,
1𝑠 2 2𝑠 2 2𝑝3
Write down the ground state electronic configuration of Copper(Z=29) (2012)
The electron configuration of copper is 1s2 2s2 2p6 3s2 3p6 4s1 3d10.
If we followed the general pattern of filling electron orbitals, we would have written
copper's electron configuration as 1s2 2s2 2p6 3s23p6 4s2 3d9. The difference is at the end
of the configuration in the 4s and 3d shells. Copper atoms have enough electrons to
completely fill the 3d sub-shell, but only if one electron from the 4s sub-shell is used. This
arrangement makes the atom more stable.
We can also write the electron configuration of copper in noble-gas-inner-core form as:

Write down the electronic configuration of Mg atom. Hence find the term symbol of its
ground state. (2015)
In ground state the electronic configuration of Mg- atom,
1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2
The term symbol can be represented as
1
𝑆0
Formula for first order nondegenerate perturbative correction to the eigenvalue statement only.

(b) Spin-orbit interaction and relativistic correction to the kinetic energy and Darwin term.

(c) Fine structure of the hydrogen atom spectrum (No rigorous derivation is required).

TIME INDEPENDENT PERTURBATION THEORY:

BASIC CONCEPT:
In the time independent perturbation approach, a known solution of a system whose
Hamiltonian is only slightly different from that of the system under consideration is used as the
starting point. The Hamiltonian operator H representing the total energy of the system can be
written as,
𝐻 = 𝐻0 + 𝐻′ … … … … … . (1)
Where 𝐻0 is call the unperturbed Hamiltonian, satisfying,
𝐻0 𝜓𝑛0 = 𝐸𝑛0 𝜓𝑛0 , 𝑛 = 1,2,3 … . (2).
whose non degenerate eigenvalues are 𝐸𝑛 corresponding to the eigenfunctions, 𝜓𝑛0 forming
0

orthogonal basis.
The perturbing operator 𝐻′is assumed to be small compare to 𝐻0 .
Our aim is to solve the Schrodinger equation,
𝐻𝜓𝑛 = 𝐸𝑛 𝜓𝑛 … … … … … … . . (3)
If we write the Hamiltonian H of the perturbed system as,
𝐻 = 𝐻0 + 𝜆𝐻′ … … … … … . . (4)
As the parameter changes from 0 to 1 the Hamiltonian changes from 𝐻0 𝑡𝑜 𝐻 and the 𝜓𝑛0 to 𝜓𝑛
Expanding 𝐸and 𝜓 in term of 𝜆,
𝑗
𝐸𝑛 = 𝐸𝑛0 + 𝜆𝐸𝑛1 + 𝜆2 𝐸𝑛2 + ⋯ = ∑ 𝜆𝑗 𝐸𝑛 … … … … (5)
𝑗

𝑗
𝜓𝑛 = 𝜓𝑛0 + 𝜆𝜓𝑛1 + 𝜆2 𝜓𝑛2 + ⋯ = ∑ 𝜆𝑗 𝜓𝑛 … … … (6)
𝑗

Here the terms with,

𝜆 = 0 𝑖𝑠 𝑐𝑎𝑙𝑙𝑒𝑑 𝑡ℎ𝑒 𝑧𝑒𝑟𝑜𝑡ℎ 𝑜𝑟𝑑𝑒𝑟 𝑡𝑒𝑟𝑚. (𝑢𝑛𝑝𝑒𝑟𝑡𝑢𝑟𝑏𝑒𝑑 𝑜𝑛𝑒)
𝜆 = 1 𝑖𝑠 𝑐𝑎𝑙𝑙𝑒𝑑 𝑡ℎ𝑒 1𝑠𝑡 𝑜𝑟𝑑𝑒𝑟 𝑡𝑒𝑟𝑚.
 𝜆 = 2 𝑖𝑠 𝑐𝑎𝑙𝑙𝑒𝑑 𝑡ℎ𝑒 2𝑛𝑑 𝑜𝑟𝑑𝑒𝑟 𝑡𝑒𝑟𝑚. and so on.
𝐸𝑛1 , 𝐸𝑛2 𝑖𝑠 𝑐𝑎𝑙𝑙𝑒𝑑 1𝑠𝑡 𝑎𝑛𝑑 2𝑛𝑑 𝑜𝑟𝑑𝑒𝑟 𝑐𝑜𝑟𝑟𝑒𝑐𝑡𝑖𝑜𝑛𝑠 𝑡𝑜 𝑡ℎ𝑒 𝑒𝑛𝑒𝑟𝑔𝑦;
𝜓𝑛1 𝑎𝑛𝑑 𝜓𝑛2 𝑎𝑟𝑒 𝑐𝑎𝑙𝑙𝑒𝑑 1𝑠𝑡 𝑎𝑛𝑑 2𝑛𝑑 𝑜𝑟𝑑𝑒𝑟 𝑐𝑜𝑟𝑟𝑒𝑐𝑡𝑖𝑜𝑛𝑠 𝑡𝑜 𝑡ℎ𝑒 𝑤𝑎𝑣𝑒𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛.
From the equation (3),
We have,
(𝐻0 + 𝜆𝐻′ )[𝜓𝑛0 + 𝜆𝜓𝑛1 + 𝜆2 𝜓𝑛2 + ⋯ ] = (𝐸𝑛0 + 𝜆𝐸𝑛1 + 𝜆2 𝐸𝑛2 + ⋯ )[𝜓𝑛0 + 𝜆𝜓𝑛1 + 𝜆2 𝜓𝑛2 + ⋯ ]
Arranging in power series of 𝜆,
𝜆0 (𝐻0 − 𝐸𝑛0 )𝜓𝑛0 +
𝜆1 (𝐻′ 𝜓𝑛0 + 𝐻0 𝜓𝑛1 − 𝐸𝑛0 𝜓𝑛1 − 𝐸𝑛1 𝜓𝑛0 ) +
𝜆2 (𝐻′ 𝜓𝑛1 + 𝐻0 𝜓𝑛2 − 𝐸𝑛0 𝜓𝑛2 − 𝐸𝑛1 𝜓𝑛1 − 𝐸𝑛2 𝜓𝑛0 ) = 0
Since 𝜆 is arbitrary the coefficient of each power of 𝜆 must vanish.
Hence ,
𝐻0 𝜓𝑛0 = 𝐸𝑛0 𝜓𝑛0 … … … … … … … … … … … … … … … . (7)
𝐻′ 𝜓𝑛0 + 𝐻0 𝜓𝑛1 = 𝐸𝑛0 𝜓𝑛1 + 𝐸𝑛1 𝜓𝑛0 … … … … … … … … . . (8)
𝐻′ 𝜓𝑛1 + 𝐻0 𝜓𝑛2 = 𝐸𝑛0 𝜓𝑛2 + 𝐸𝑛1 𝜓𝑛1 + 𝐸𝑛2 𝜓𝑛0 … … . … … (9)

NON-DEGENERATE ENERGY LEVEL:

1ST order correction to the energy:
Multiplying the equation (8) from the left by ⟨𝜓𝑛0 |, we get,
⟨𝜓𝑛0 |𝐻′ |𝜓𝑛0 ⟩ + ⟨𝜓𝑛0 |𝐻0 |𝜓𝑛1 ⟩ = 𝐸𝑛1 ⟨𝜓𝑛0 |𝜓𝑛0 ⟩ + 𝐸𝑛0 ⟨𝜓𝑛0 |𝜓𝑛1 ⟩ … … . (10)
Now
⟨𝜓𝑛0 |𝜓𝑛1 ⟩ = 0
As H hermitian,
⟨𝜓𝑛0 |𝐻0 |𝜓𝑛1 ⟩ = 𝐸𝑛0 ⟨𝜓𝑛0 |𝜓𝑛1 ⟩ = 0
⟨𝜓𝑛0 |𝐻0 |𝜓𝑛0 ⟩ = 𝐸𝑛1
Hence,
𝐸𝑛1 = ⟨𝜓𝑛0 |𝐻′ |𝜓𝑛0 ⟩ … … … (11)
The 1st order correction to the energy is thus the average value of the perturbation over the
corresponding unperturbed states of the system.

1ST order correction to the wave function :

0
Multiplying the equation (8) from the left by ⟨𝜓𝑚 |, we get,
0 |𝐻 ′ |𝜓 0 ⟩
⟨𝜓𝑚 0 0 1 1 0 0 0 0 1
𝑛 + ⟨𝜓𝑚 |𝐻 |𝜓𝑛 ⟩ = 𝐸𝑛 ⟨𝜓𝑚 |𝜓𝑛 ⟩ + 𝐸𝑛 ⟨𝜓𝑚 |𝜓𝑛 ⟩ … … . (12)

let us represent the 1st order correction to the wave function as the linear combination of the
unperturbed wave functions as,

𝜓𝑛1 = ∑ 𝑎𝑗 𝜓𝑗0 … … … … … … . (13)

𝑗

Hence from the equation (8)

0 |𝐻 ′ |𝜓 0 ⟩ 0 0 0 1 0 0 0 0 0
⟨𝜓𝑚 𝑛 + ∑ 𝑎𝑗 ⟨𝜓𝑚 |𝐻 |𝜓𝑗 ⟩ = 𝐸𝑛 ⟨𝜓𝑚 |𝜓𝑛 ⟩ + 𝐸𝑛 ∑ 𝑎𝑗 ⟨𝜓𝑚 |𝜓𝑗 ⟩ … … (13)
𝑗 𝑗

Now
0 |𝐻 0 |𝜓 0 0 0 0 0 0
∑ 𝑎𝑗 ⟨𝜓𝑚 𝑗 ⟩ = ∑ 𝑎𝑗 𝐸𝑗 ⟨𝜓𝑚 |𝜓𝑗 ⟩ = ∑ 𝑎𝑗 𝐸𝑗 𝛿𝑚𝑗 = 𝑎𝑚 𝐸𝑚
𝑗 𝑗 𝑗

Due to ortho normality,

0 |𝜓 0 ⟩
⟨𝜓𝑚 𝑛 =0

Hence,
0 |𝐻 ′ |𝜓 0 ⟩
⟨𝜓𝑚 0 0
𝑛 + 𝑎𝑚 𝐸𝑚 = 𝑎𝑚 𝐸𝑛

Hence,
0 |𝐻 ′ |𝜓 0 ⟩
⟨𝜓𝑚 ⟨𝑚|𝐻′ |𝑛⟩
𝑛
𝑎𝑚 = =
𝐸𝑛0 − 𝐸𝑚
0
𝐸𝑛0 − 𝐸𝑚
0

Hence,
⟨𝑚|𝐻′ |𝑛⟩
𝜓𝑛1 = 0
∑ 𝑎𝑚 |𝜓𝑚 ⟩ =∑ 0
|𝜓𝑚 ⟩
𝐸𝑛0 − 0
𝐸𝑚
𝑚 𝑚

So the energy and wavefunction,

𝐸𝑛 = 𝐸𝑛0 + ⟨𝑛|𝐻0 |𝑛⟩
 ⟨𝑚|𝐻′ |𝑛⟩
𝜓𝑛 = 𝜓𝑛0 +∑ 0
|𝜓𝑚 ⟩
𝐸𝑛0 − 0
𝐸𝑚
𝑚

Q1: Consider the following 1D potential box in both cases the energy lever is raised by 𝑉0 .
Calculate the 1st order correction term.
Here

𝐻′ = 𝑉0 .
Hence
𝐸 ′ = ⟨𝜓01 |𝑉0 |𝜓01 ⟩ = 𝑉0
But in the 2nd case,
𝑎
2
2 𝑛𝜋 𝑉0
𝐸 ′ = ⟨𝜓01 |𝐻′|𝜓01 ⟩ = ∫ sin2 ( 𝑥) 𝑉0 𝑑𝑥 =
𝑎 𝑎 2
0

Which is surprisingly equal to

𝑉0 1
⟨𝜓01 | |𝜓 ⟩
2 0
Clearly the 2nd one not the exact result. We need higher order correction terms.

2. Suppose we put a delta-function potential, in the centre of the infinite potential well as
𝑎
𝐻′ = 𝛼𝛿 (𝑥 − )
2
st
i) Find the 1 order correction to the allowed energies.
ii) Find the correction of the ground state wave function (up to 3 terms)

i) we have,
𝑎
2 𝑛𝜋 𝑎 2𝛼 2 𝑛𝜋
𝐸 ′ = ⟨𝜓10 |𝐻′|𝜓10 ⟩ = ∫ sin2 ( 𝑥) 𝛼𝛿 (𝑥 − ) 𝑑𝑥 = sin ( )
𝑎 𝑎 2 𝑎 2
0

2𝛼
𝑐𝑙𝑒𝑎𝑟𝑙𝑦 𝐸 ′ = 𝑓𝑜𝑟 𝑛 = 𝑜𝑑𝑑
𝑎
= 0 𝑓𝑜𝑟 𝑛 = 𝑒𝑣𝑒𝑛;
as the wave function is always zero at the centre hence don’t care of 𝐻′.

ii) Here 𝑛 = 1,
𝑎
0 |𝐻′|𝜓 0 ⟩
2 𝑚𝜋 𝑎 𝜋
⟨𝜓𝑚 1 = ∫ 𝑠𝑖𝑛 ( 𝑥) 𝛼𝛿 (𝑥 − ) 𝑠𝑖𝑛 ( 𝑥) 𝑑𝑥
𝑎 𝑎 2 𝑎
0
2𝛼 𝑚𝜋 𝜋
= 𝑠𝑖𝑛 ( ) sin
𝑎 2 2
2𝛼 𝑚𝜋
= 𝑠𝑖𝑛 ( )
𝑎 2
0 |𝐻 ′ |𝜓 0 ⟩
⟨𝜓𝑚 1
𝜓11 = ∑ 0
𝜓𝑚
𝐸10 − 0
𝐸𝑚
𝑚=1
2𝛼 𝑚𝜋
𝑠𝑖𝑛 ( )
= ∑ 𝑎 2 𝜓0
(1 − 𝑚 )𝐸12 𝑚
2
𝑚=1
𝑚𝜋
2𝛼 8𝑚0 𝑎2 𝑠𝑖𝑛 ( )
= × ∑ 2 (𝜓 0 )
2 𝑚
𝑎 ℎ 1 − 𝑚2
𝑚=1

3𝜋 5𝜋 7𝜋
16𝑚0 𝑎 𝛼 𝑠𝑖𝑛 ( 2 ) 0 𝑠𝑖𝑛 ( 2 ) 0 𝑠𝑖𝑛 ( 2 ) 0
= ( 𝜓3 + 𝜓5 + 𝜓7 )
ℎ2 1 − 32 1 − 52 1 − 72

16𝑚0 𝑎 𝛼 1 0 1 0 1 0
= ( 𝜓3 − 𝜓 + 𝜓 )
ℎ2 8 24 5 48 7
16𝑚0 𝑎 𝛼 1 0 1 0 1 0
= ( 𝜓3 − 𝜓 + 𝜓 )
ℎ2 8 24 5 48 7

8𝑚0 𝑎𝛼 2 3𝜋 1 5𝜋 1 5𝜋
= √ (sin 𝑥 − sin 𝑥 + sin 𝑥)
ℎ2 𝑎 𝑎 3 𝑎 6 𝑎
 4𝑚0 𝛼 𝑎 3𝜋 1 5𝜋 1 5𝜋
= √ (sin 𝑥 − sin 𝑥 + sin 𝑥)
ℎ2 2 𝑎 3 𝑎 6 𝑎

Fine structure of Hydrogen atom:

NOTE:

1. The relativistic expression for the kinetic energy of the electron,

𝐸𝑘 = 𝑚𝑐 2 − 𝑚0 𝑐 2
= √𝑝2 𝑐 2 + 𝑚02 𝑐 4 − 𝑚0 𝑐 2
1
𝑝 2 2
= 𝑚0 𝑐 2 [1 + ( ) ] − 𝑚0 𝑐 2
𝑚0 𝑐
2
1 𝑝 2 1 𝑝 4
= 𝑚0 𝑐 [1 + ( ) − ( ) + ⋯ ] − 𝑚0 𝑐 2
2 𝑚0 𝑐 8 𝑚0 𝑐
𝑝2 1 𝑝4
= −
2𝑚 8 𝑚03 𝑐 2
Hence the correction term,

𝑝4
𝐻1′ =−
8𝑚3 𝑐 2

2. Spin orbit coupling: The spin of the electron and its associated magnetic moment
change the interaction of the electron with the electric field due to nucleus.
An electron moving with uniform velocity 𝑣⃗ experiences magnetic field,
𝑣⃗ × 𝐸⃗⃗ −𝛻⃗⃗ ∅ 1 𝑑𝜙 1 𝑑𝜙 1 1 𝑑𝜙 1
⃗⃗ =
𝐵 = 𝑣 × 2 = − 2 𝑣⃗ × 𝑟̂ = − 2 𝑣⃗ × 𝑟⃗ = − 𝑚𝑣⃗ × 𝑟⃗ =
𝑐 𝑐 𝑐 𝑑𝑟 𝑐 𝑑𝑟 𝑟 𝑚𝑐 2 𝑑𝑟 𝑟
1 𝑑𝜙 1
= 2
𝑙⃗
𝑚𝑐 𝑑𝑟 𝑟

∅ is the potential at the position of electron due to nucleus

𝑍𝑒
=
4𝜋𝜖0 𝑟
Due to spin the magnetic moment of the electron,
 𝑒
𝜇𝑠 = − 𝑆⃗
𝑚

Corresponding interaction energy,

𝑒 1 𝑑𝜙 1 𝑒 𝑑𝜙 1
⃗⃗ =
𝜖𝑙𝑠 = −𝜇⃗ ∙ 𝐵 𝑆⃗ ∙ ⃗=
𝑙 𝑙⃗ ∙ 𝑠⃗
𝑚 𝑚𝑐 2 𝑑𝑟 𝑟 𝑚2 𝑐 2 𝑑𝑟 𝑟
1
A new perturbating term due to non-linear motion of electron additional factor term is
2
introduced thus ,
𝑍𝑒 2 1
𝐻2′ = 𝑙⃗ ∙ 𝑠⃗ = 𝑓(𝑟)𝑙⃗ ∙ 𝑠⃗
8𝜋𝜖0 𝑚2 𝑐 2 𝑟 3

3. The ``Darwin Term'' correction to s states from Dirac eq.

Such a correction would arise from a nonlocal correction to the potential energy term. It is as
if the electron had grown from point-like to a ball with radius of order its Compton wavelength
ℏ
. The potential energy due to the field of the proton must then be calculated by integrating
𝑚0 𝑐
the varying electric potential over the charge distribution of the electron.
The Darwin term affects only the s orbitals. This is because the wave function of an electron
with 𝑙 > 0 vanishes at the origin, hence the delta function has no effect.

The total Hamiltonian for the electron in hydrogen like atom,

𝐻 = 𝐻0 + 𝐻′
𝑝2
Where 𝐻0 = + 𝑉(𝑟) is the unperturbed term and 𝐻′ can be
2𝑚
regarded as the perturbation given be
𝐻′ = 𝐻1′ + 𝐻2′ + 𝐻3 ′
𝑝4
𝐻1′
=−
8𝑚3 𝑐 2
1 1 𝑑𝑉
𝐻2′ = 𝑳∙𝑺
2𝑚2 𝑐 2 𝑟 𝑑𝑟
𝜋ℏ2 𝑍𝑒 2
𝐻3′ = ( ) 𝛿(𝑟)
2𝑚2 𝑐 2 4𝜋𝜖0
𝐻1′ , 𝐻2′ are called relativistic corrections due to kinetic energy, the spin orbit interaction
and 𝐻3′ is the Darwin term.
Effect of 𝑯𝟏
 The 1st order energy correction due to the 𝐻1′ ,

𝑝4
∆𝐸𝑛𝑙 = ⟨𝑛|𝐻1′ |𝑛⟩ = ⟨𝑛 |− | 𝑛⟩
8𝑚3 𝑐 2
2
1 𝑝2
=− ⟨𝑛 |− ( ) | 𝑛⟩
2𝑚𝑐 2 2𝑚

1 2
=− 2
⟨𝑛 |(𝐻0 − 𝑉(𝑟)) | 𝑛⟩
2𝑚𝑐
1
=− [⟨𝑛|𝐻02 |𝑛⟩ + ⟨𝑛|𝑉02 |𝑛⟩ − ⟨𝑛|𝐻0 𝑉(𝑟)|𝑛⟩ − ⟨𝑛|𝑉(𝑟)𝐻0 |𝑛⟩]
2𝑚𝑐 2

Now
𝑖) ⟨𝑛|𝐻02 |𝑛⟩ = 𝐸𝑛2
2
1 𝑍𝑒 2
𝑖𝑖)⟨𝑛|𝑉02 |𝑛⟩ = ⟨𝑛| (−
4𝜋𝜖0 𝑟 ) |𝑛⟩
2
1 2 1
=( 𝑍𝑒 ) ⟨𝑛| 2 |𝑛⟩
4𝜋𝜖0 𝑟
2
1 2
𝑍2
=( 𝑍𝑒 ) { }
4𝜋𝜖0 2 3 1
𝑎0 𝑛 (𝑙 + )
2
𝑖𝑖𝑖) − ⟨𝑛|𝐻0 𝑉(𝑟)|𝑛⟩ − ⟨𝑛|𝑉(𝑟)𝐻0 |𝑛⟩
= −2𝐸𝑛 ⟨𝑛|𝑉(𝑟)𝐻0 |𝑛⟩
1 𝑍𝑒 2
= 2𝐸𝑛 ⟨𝑛|
4𝜋𝜖0 𝑟 |𝑛⟩
1 1
= 2𝐸𝑛 𝑍𝑒 2 ⟨𝑛| |𝑛⟩
4𝜋𝜖0 𝑟
1 𝑍
= 2𝐸𝑛 𝑍𝑒 2 { }
4𝜋𝜖0 𝑎0 𝑛2
Hence considering all terms together,

(𝑍𝛼)2 𝑛 3
∆𝐸𝑛𝑙 = ⟨𝑛|𝐻1′ |𝑛⟩ = 𝐸𝑛 ( − )
𝑛2 1 4
𝑙+
2
Note:
 𝑎0 = 𝐵ℎ𝑜𝑟 𝑟𝑎𝑑𝑖𝑢𝑠;
1 𝑒2
𝛼=
4𝜋𝜖0 ℏ𝑐
𝑚𝑍 2 𝑒 4
𝐸𝑛 = −
32𝜋 2 ℏ2 𝜖02 𝑛2
𝑚𝑐 2 (𝑍𝛼)2
=−
2𝑛2

Effect of the spin orbit term:

the spin orbit energy term can be written as,
1 1 𝑑𝑉 1 𝑍𝑒 2 1
𝐻2′ = 𝑳∙𝑺= 𝑳 ∙ 𝑺 = 𝑓(𝑟) 𝑳 ∙ 𝑺
2𝑚2 𝑐 2 𝑟 𝑑𝑟 2𝑚2 𝑐 2 4𝜋𝜖0 𝑟 3
From the addition of angular momenta,
3
𝑗(𝑗 + 1) − 𝑙(𝑙 + 1) −
𝑳∙𝑺= 4
2
1 𝑍𝑒 2 1
∆𝐸𝐿𝑆 = ⟨𝑛|𝐻2′ |𝑛⟩ = ⟨𝑛 | 2 2 𝑳 ∙ 𝑺| 𝑛⟩
2𝑚 𝑐 4𝜋𝜖0 𝑟 3
1 𝑍𝑒 2 1
= ⟨𝑛 | 𝑳 ∙ 𝑺| 𝑛⟩
2𝑚2 𝑐 2 4𝜋𝜖0 𝑟3
1 𝑍𝑒 2 1
= ⟨𝑛 | 𝑳 ∙ 𝑺| 𝑛⟩
2𝑚2 𝑐 2 4𝜋𝜖0 𝑟3
1 𝑍𝑒 2 1
= ⟨𝑛 | | 𝑛⟩ ⟨𝑛| 𝑳 ∙ 𝑺|𝑛⟩
2𝑚2 𝑐 2 4𝜋𝜖0 𝑟3

3
1 𝑍𝑒 2 𝑍3 𝑗(𝑗 + 1) − 𝑙(𝑙 + 1) −
= { }[ 4]
2 2 1
2𝑚 𝑐 4𝜋𝜖0 (𝑎 )3 𝑛3 𝑙 (𝑙 + ) (𝑙 + 1) 2
0 2
This term vanishes for 𝑙 = 0
Note :

1 𝑍𝑒 2 𝑍3 (𝑍𝛼)2
(∆𝐸𝐿𝑆 ) 1 = { } [𝑙] = −𝐸𝑛
𝑗=𝑙+
2 2𝑚2 𝑐 2 4𝜋𝜖0 𝑎3 𝑛3 𝑙 (𝑙 + 1) (𝑙 + 1) 1
2𝑛 (𝑙 + ) (𝑙 + 1)
0 2 2
 1 𝑍𝑒 2 𝑍3 (𝑍𝛼)2
(∆𝐸𝐿𝑆 ) 1 = { } [−(𝑙 + 1)] = 𝐸𝑛
𝑗=𝑙−
2 2𝑚2 𝑐 2 4𝜋𝜖0 𝑎3 𝑛3 𝑙 (𝑙 + 1) (𝑙 + 1) 1
2𝑛𝑙 (𝑙 + )
0 2 2

(𝒄)Effect of the Darwin term:

𝜋ℏ2 𝑍𝑒 2 (𝑍𝛼)2
ΔEd = ⟨𝑛|𝐻3′ |𝑛⟩ = ( ) ⟨𝜓𝑛00 |𝛿(𝑟)|𝜓𝑛00 ⟩ = −𝐸𝑛
2𝑚2 𝑐 2 4𝜋𝜖0 2

Combining all terms together we can have,

(𝑍𝛼)2 𝑛 3
Δ𝐸𝑛𝑙 + Δ𝐸𝑙𝑠 + Δ𝐸𝑑 = 𝐸𝑛 ( − )
𝑛2 1 4
𝑗+
2
Thus
Total energy including the fine structure constant,

(𝑍𝛼)2 𝑛 3
𝐸𝑛𝑗 = 𝐸𝑛 + Δ𝐸𝑛𝑗 = 𝐸𝑛 [1 + ( − )]
𝑛2 1 4
𝑗+
2

The splitting of the 𝛼𝑙𝑖𝑛𝑒 𝑜𝑓 𝑡ℎ𝑒 𝐵𝑎𝑙𝑚𝑒𝑟 𝑠𝑒𝑟𝑖𝑒𝑠 𝑖𝑠 𝑠ℎ𝑜𝑤𝑛 ℎ𝑒𝑟𝑒.