Lecture 20 - PH20013

The states ∣ℓ − s∣ ≤ j ≤ ℓ + shave slightly different energy to each other. This is

seen in the fine structure of the atomic spectra.
For example, in sodium lights, we observe 2 different beams when excited to a 3p
state. This is because we have j = 12 , 32 with different energies.
​ ​

Consider the frame of reference of the electron. The electron will be at rest, with
the nucleus orbiting it. This nucleus has atomic number Z , and takes τ time to
make a full loop of radius r . Therefore the current is:

Ze
I= ​

τ
This produces a magnetic field exactly in the centre of the orbit - the electron:

μ0 I μ0 Ze
B= = n
^
​ ​

2r 2r τ
​ ​ ​

We can express this in terms of angular momentum:

μ0 Ze
B= L
​

4πmr 3
​

This is the strength of the magnetic field generated exactly where the electron is
due to the orbiting nucleus.
The spin magnetic moment will interact with this field. This has an energy:

Eso = −μs ⋅ B
​ ​

ZμB
= S⋅B
​

ℏ
​

Substituting everything in:

μB μ0 Z e 1
Eso = ( 3)S ⋅ L
​ ​

2πℏm
​ ​ ​

Lecture 20 - PH20013 1
 Using the expectation value for the radius term:

3
1 1
( )
Z
∼
r3 n3
​ ​ ​

a0 ​

Let us then square the total angular momentum:

J = (L + S)2
=
= L + S2 + 2L ⋅ S
2

J2 − L2 − S2
L⋅S=
2
​

However, we know these squared values:

J2 = ℏ2 j(j + 1)
L2 = ℏ2 ℓ(ℓ + 1)
S2 = ℏ2 s(s + 1)

We then impose the fact that these values are quantised. Therefore:

Z4
∼( ) ( 3 ) (j(j + 1) − ℓ(ℓ + 1) − s(s + 1))
μB μ0 eℏ
​ ​

Eso
ma30
​ ​ ​

n ​

Let us consider the hydrogen 2pstate. We have:

1 1 3
ℓ = 1, s = ∴j= ,
2 2 2
​ ​ ​

For j = 12 :
​

Eso = C(j(j + 1) − ℓ(ℓ + 1) − s(s + 1))

​

3 3
=C( −2− )
4 4
​ ​

= −2C

The state is slightly lowered by an energy of −2C . For j = 32 :

​

Lecture 20 - PH20013 2
 Eso = +C
​

The energy is slightly higher. Therefore:

ΔE = 3C
∼ 1 × 10−4 eV

This is very small for an atom with Z = 1.

It turns out that spin also affects the nucleons, and as such they can interact
further, which creates hyperfine structure.
By definition of the states, a 2sstate (ℓ = 0) will have no splitting into different j 
numbers. Therefore, we expect no energy difference - it is the only state.

As before, we will have a total magnetic moment as well. We know the orbital
magnetic moment us:

gL μB
μL = − L
​ ​

ℏ
​

And the spin magnetic moment:

gS μB
μS = − S
​ ​

ℏ
​ ​

By analogy we have:

gJ μB
μJ = − J
​ ​

ℏ
​

Lecture 20 - PH20013 3
 where:

3j(j + 1) − ℓ(ℓ + 1) + s(s + 1)

gJ =
2j(j + 1)
​ ​

If we have s = 0, j = ℓ, gJ = 1and for ℓ = 0, j = s, gJ = 2

​ ​

WRITE THESE ABOVE DOWN ON THE CHEAT SHEET

Lecture 20 - PH20013 4