Fine-Structure

• It is observed in the sodium spectrum that D-line (yellow emission) is

split into two lines D1 = 5895.93 Å or 589.59 nm, D2 = 5889.9 Å or 588.99
nm.
• The reason of observing this doublet is that the energy levels split into
two for the terms except s-level (l = 0).
• Many lines of the other alkali atoms are also doublets.
• With high resolution spectrometer shows that even hydrogen atom lines
are also having this doublet nature.
• The Coulomb interactions between the nucleus and electron in the
outermost orbit for alkali atoms can not explain this observation
• Not only alkali atoms, but also in the other multielectron atoms the
transitions between the terms split into more number of transitions.
This is known as Fine structure.
• The cause of this fine structure is the interaction between the orbital
angular momentum and the spin angular momentum.
• We will review the origin for this interaction and the effect of the
coupling between orbital and spin on the spectral lines and discuss here
mainly hydrogen atom and also the other alkali atoms.
Magnetic Moment of the Orbital Motion
• From classical electrodynamics, a rotating electrically
charged body creates a magnetic dipole with magnetic
poles of equal magnitude but opposite polarity.
• Consider that an electron is moving with velocity V in a
circular Bohr orbit of radius r that produces a current.
This current loop will produce a magnetic field with the
magnetic moment,
𝑒𝜔 2 1
𝜇𝑙 = 𝑖𝐴 = − 𝜋𝑟 = − 𝑒𝜔𝑟 2
2𝜋 2
𝑒𝜔
where 𝑖 = , 𝜔 is the angular velocity, A is the area.
2𝜋
• Magnitude of the orbital angular momentum
𝑙 = 𝑚𝑣𝑟 = 𝑚𝜔𝑟 2
• Substituting we get , the orbital magnetic moment
𝑒
𝜇𝑙 = − 𝑙
2𝑚
• Now the Bohr Magneton is defined as the magnetic
moment of the first Bohr orbital. So,
𝑒ℏ
the Bohr Magneton 𝜇𝐵 = − = 9.27 × 10−24 J/T
2𝑚
• The Orbital magnetic moment in terms of Bohr magneton is thus, in the
vector form
𝑔𝑙 𝜇𝐵 Ԧ
𝜇𝑙 = − 𝑙 with 𝑔𝑙 = 1
ℏ
• Substituting the value of the angular momentum
𝜇𝐵
𝜇𝑙 = ℏ 𝑙(𝑙 + 1) = 𝜇𝐵 𝑙(𝑙 + 1)
ℏ
• Along the Z-direction, the component of , so 𝑙𝑧 = 𝑚𝑙 ℏ
𝜇𝐵
𝜇𝑙𝑧 = − 𝑙z = −𝜇𝐵 𝑚𝑙
ℏ
Relations of L, S and J 𝑔𝑙 𝜇𝐵
𝜇𝑙 = − 𝑙Ԧ with 𝑔𝑙 = 1
ℏ

𝜇𝐵
𝜇𝑙 = ℏ 𝑙(𝑙 + 1) = 𝜇𝐵 𝑙(𝑙 + 1)
ℏ
𝜇𝐵
𝜇𝑙𝑧 = − 𝑙 = −𝜇𝐵 𝑚𝑙 𝑚𝑙 = + 𝑙 to - 𝑙
ℏ z

𝑒 𝑔𝑠 𝜇𝐵
𝜇𝑠 = −𝑔𝑠 𝑠Ԧ 𝑜𝑟 𝜇𝑠 = − 𝑠Ԧ with spin Lande g-factor gs =2.0023
2𝑚 ℏ

|𝑠| = ℏ 𝑠(𝑠 + 1) with s = 1/2

𝜇𝑠 𝑧 = −𝑔𝑠 𝜇𝐵 𝑚𝑠 𝑚𝑠 = +1/2 or -1/2

𝑔𝑗 𝜇𝐵
𝜇𝑗 = − 𝑗Ԧ
ℏ

with total angular momentum J Lande g-factor gJ = in terms of L and S

j has the magnitude ℏ 𝑗(𝑗 + 1) with 𝑗 = |𝑙 ± 𝑠|

𝑔𝑗 𝜇𝐵
𝜇𝑗𝑧 = − 𝑗z = −𝜇𝐵 𝑔𝑗 𝑚𝑗 𝑚𝑗 = + j to - j
ℏ
Continue…

• When this dipole moment is placed in an external

magnetic field along the Z-direction, it experiences a
torque which can be expressed as 𝜏Ԧ = 𝜇Ԧ × 𝐵.
• The potential energy ∆𝐸 = −𝜇Ƹ ⋅ 𝐵෠
• For a static magnetic moment, this torque tends to line up
the magnetic moment with the magnetic field B, so that it
reaches its lowest energy configuration.
• The magnetic moment arises from the motion of an
electron in orbit around a nucleus and the magnetic
moment is proportional to the angular momentum of the
electron.
• The torque exerted then produces a change in angular
momentum. This change is perpendicular to that angular
momentum, causing the magnetic moment to precess
around the direction of the magnetic field rather than
settle down in the direction of the magnetic field.
• This precession is known as Larmor precession.
• When a torque is exerted perpendicular to the angular
momentum l, it produces a change in angular momentum
Δl which is perpendicular to l. Referring to figure , .
• the torque is given by,

we get

This is known as Larmor frequency.

 Spin and Magnetic Moment of the Electron
• The s states with orbital angular momentum l = 0 have no orbital
magnetic moment.
• Therefore, a one-electron atom should be diamagnetic in the ground
state, when it has one valence electron in an outer shell and all the
others in closed shells.
• However, these atoms are actually paramagnetic.
• The reason is the existence of electron spin and the associated magnetic
moment.
• Electron spin was introduced by Uhlenbeck and Goudsmit in 1925 to
explain spectroscopic observations.
• The electron has a spin angular momentum s,
|𝑠| = ℏ 𝑠(𝑠 + 1)
• The associated magnetic moment
𝑒
𝜇𝑠 = −𝑔𝑠 𝑠Ԧ
2𝑚
where e is again the unit charge of the electron, without the negative sign.
s = 1/2 is a new quantum number, the spin quantum number.
Spin magnetic moment :
• electron also produces the magnetic moment due to the spin angular momentum.
The spin dipole moment, in terms of spin Lande g-factor gs =2.0023
𝑔𝑠 𝜇𝐵
𝜇𝑠 = − 𝑠Ԧ
ℏ
𝜇𝑠 𝑧 = −𝑔𝑠 𝜇𝐵 𝑚𝑠
𝜇𝑠 𝑧 is the component in the Z direction
• The gyromagnetic ratio, which is defined as the ratio between the magnetic moment
and the angular momentum, is thus not the same for orbital and spin magnetism.
• For pure orbital magnetism,
• For pure spin magnetism
Detection of Directional Quantisation by Stern
and Gerlach
• In 1921, the deflection of atomic beams in inhomogeneous magnetic
fields made possible
• - the experimental demonstration of directional quantisation and
• - the direct measurement of the magnetic moments of atoms.
• The deflecting force can be derived from the
potential energy in the magnetic field
𝑉𝑚𝑎𝑔 = −𝝁 ⋅ 𝑩
𝑑𝐵 𝑑𝐵
𝐹𝑍 = 𝜇𝑧 =𝜇 cos 𝛼
𝑑𝑧 𝑑𝑧

where 𝛼 is the angle between the magnetic moment

and the direction of the field gradient.
• This experiment and similar measurements on other atoms permit the
following conclusions:
• There is a directional quantisation. There are only discrete possibilities
for the orientation relative to a field B0, in this case two, parallel and
antiparallel.
• From a quantitative evaluation of the observed deflection d in the above
example, one obtains the value 𝜇𝑧 = ±𝜇𝐵 . In general this method
provides observed values for atomic magnetic moments if the
magnitude of the field gradient is known.
• For all atoms which have an s electron in the outermost position, one
obtains the same value for the deflecting force, from which it follows
that the angular momenta and magnetic moments of all inner electrons
cancel each other and one measures only the effect of the outermost s
electron.
• The s electron has an orbital angular momentum l = 0 and one observes
only spin magnetism.
• Like gyroscopes, atoms maintain the magnitude and direction of their
angular momenta in the course of their motion in space.
Fine Structure and Spin-Orbit Coupling: Overview

• The doublet or multiplet structure of the spectral lines,

is denoted by the generic name fine structure.
• The fine structure cannot be explained with the
Coulomb interaction between the nucleus and the
electrons.
• It results from a magnetic interaction between the
orbital magnetic moment and the intrinsic moment of
the electron, the spin-orbit coupling.
• Depending on whether the two moments are parallel
or antiparallel, the energy term is shifted somewhat.
• The coupling of the magnetic moments leads to an
addition of the two angular momenta to yield a total
angular momentum.
• l and s add to give a total angular
momentum j;
• j has the magnitude ℏ 𝑗(𝑗 + 1) with
1
𝑗 = |𝑙 ± 𝑠| i.e. 𝑗 = |𝑙 ± | for the case
2
treated here of a single-electron system
with s = 1/2.
• The quantum number j is the quantum
number of the total angular
momentum.
• For a p electron with l = 1, s = 1/2, we
find the following possibilities:
• when l = 0, j = s and there is no doublet splitting; for j, just
as for l, there is a directional quantisation. The z
components must obey the condition
• 𝑗𝑧 = 𝑚𝑗 ℏ, 𝑚𝑗 = 𝑗, 𝑗 − 1, … , −𝑗 (2𝑗 + 1 possibilities)
Relations of L, S and J 𝑔𝑙 𝜇𝐵
𝜇𝑙 = − 𝑙Ԧ with 𝑔𝑙 = 1
ℏ

𝜇𝐵
𝜇𝑙 = ℏ 𝑙(𝑙 + 1) = 𝜇𝐵 𝑙(𝑙 + 1)
ℏ
𝜇𝐵
𝜇𝑙𝑧 = − 𝑙 = −𝜇𝐵 𝑚𝑙 𝑚𝑙 = + 𝑙 to - 𝑙
ℏ z

𝑒 𝑔𝑠 𝜇𝐵
𝜇𝑠 = −𝑔𝑠 𝑠Ԧ 𝑜𝑟 𝜇𝑠 = − 𝑠Ԧ with spin Lande g-factor gs =2.0023
2𝑚 ℏ

|𝑠| = ℏ 𝑠(𝑠 + 1) with s = 1/2

𝜇𝑠 𝑧 = −𝑔𝑠 𝜇𝐵 𝑚𝑠 𝑚𝑠 = +1/2 or -1/2

𝑔𝑗 𝜇𝐵
𝜇𝑗 = − 𝑗Ԧ
ℏ

with total angular momentum J Lande g-factor gJ = in terms of L and S

j has the magnitude ℏ 𝑗(𝑗 + 1) with 𝑗 = |𝑙 ± 𝑠|

𝑔𝑗 𝜇𝐵
𝜇𝑗𝑧 = − 𝑗z = −𝜇𝐵 𝑔𝑗 𝑚𝑗 𝑚𝑗 = + j to - j
ℏ
Calculation of Spin-Orbit Splitting in the Bohr Model
• We shall calculate the energy difference between the parallel and the
antiparallel orientations of the orbital angular momentum and the spin.
• The motion of the electron around the nucleus generates a magnetic
field Bl at the site of the electron. This field interacts with the magnetic
moment of the electron.
• To determine the magnitude of this magnetic field, we borrow from
relativity theory and assume that the electron is stationary and that the
nucleus moves instead
 • The magnetic field of the moving charge + Ze is found from the Biot-
Savart law to be

OR

• Angular momentum is defined as 𝒍 = 𝒓 × 𝑚0 𝒗. Then

The magnetic field which is generated by the relative motion of the nucleus
and the electron is thus proportional and parallel to the orbital angular
momentum of the electron.
We still require the back transformation to the centre-of-mass system of the
atom, in which the nucleus is essentially at rest and the electron orbits around
it.
A factor 1/2 occurs in this back transformation, the so-called Thomas factor,
which can only be justified by a complete relativistic calculation.
• The magnetic moment of the electron, and with it, its
coupled spin vector, precess about the magnetic field Bl
produced by the orbital motion.
• The interaction energy between the spin and the orbital
field is thus

as
Thomas correction included

Rewriting

Vector addition
of the angular
momentum
vectors to the
total angular
momentum
• there are no fixed orbits in the quantum theoretical
description of the atom.
• Therefore,
1 𝑍3
•< >= 1 , for 𝑙 > 0
𝑟3 𝑎03 𝑛3 𝑙 𝑙+ (𝑙+1)
2
 Spin-orbit interaction energy for alkali atoms
• Using perturbation theory, spin-orbit interaction energy is given
by
• ∆𝐸𝑆𝑂 = 𝑗 𝑚𝑗 𝑉𝑙,𝑠 𝑗 𝑚𝐽
𝐴𝑆𝑂
• ∆𝐸𝑆𝑂 = (𝑗 𝑗+1 −𝑙 𝑙+1 −𝑠 𝑠+1 )
2
• Let us first look at the Sodium energy levels.
• Similar to sodium atom, Hydrogen atom also shows doublet.
• Spectral lines of H found to be composed of closely spaced doublets.
• Splitting is due to interactions between electron spin s and the orbital
angular momentum l.
• Hα line is single line according to the Bohr or Schrödinger theory, occurs
at 656.47 nm for Hydrogen and 656.29 nm for Deuterium (isotope shift,
Δλ~0.2 nm).
• Spin-orbit coupling produces fine-structure splitting of ~0.016 nm
corresponds to an internal magnetic field on the electron of about 0.4
Tesla.
• Orbital and spin angular momenta couple together via the spin-orbit
interaction Internal magnetic field produces torque which results in
precession of l and s about their sum, the total angular momentum:
• This kind of coupling is called L-S coupling or Russell-Saunders coupling
 Relativistic kinetic energy correction :
• According to special relativity, the kinetic energy of an electron of mass
m0 and velocity v is:
𝑝2 𝑝4
𝑇≈ − , where p is the momentum
2𝑚0 8𝑚03 𝑐 2

• The first term is the standard non-relativistic expression for kinetic

energy. The second term is the lowest-order relativistic correction to
this energy.
• Using perturbation theory, it can be shown that
𝑍 2 𝛼4 1 3
∆𝐸𝑟𝑒𝑙 = − 3 𝑚0 𝑐 2 − .
𝑛 2𝑙+1 8𝑛
• This energy correction does not split the energy levels, it only produces
an energy shift comparable to spin-orbit effect.
• So the total energy correction for the fine structure
𝑍 2 𝐸0 𝛼2 𝑍 2 1 3
𝐸𝑛,𝑙,𝑗 = 𝐸𝑛,𝑙 + ∆𝐸𝑆𝑂 + ∆𝐸𝑟𝑒𝑙 = − 2 1+ 1 −
𝑛 𝑛 𝑗+ 4𝑛
2

• Where 𝐸0 = −13.6 𝑒𝑉
 𝛼 2 𝑍 4 𝐸0 1 3
Fine-structure of H atom: EFS = − 1 −
𝑛3 𝑗+ 4𝑛
2
 The Lamb Shift

• In the years 1947 -1952, Lamb

and Retherford showed that
even the relativistic Dirac
theory did not completely
describe the H atom.
• They used the methods of
high-frequency and microwave
spectroscopy to observe very
small energy shifts and
splitting in the spectrum of
𝛼 2 𝑍 4 𝐸0 1 3
atomic hydrogen. EFS =− −
1 4𝑛
𝑛3 𝑗+
2
The Lamb shift: fine structure of n = 2 level in the H
atom according to Bohr, Dirac and quantum
electrodynamics taking into account the Lamb shift.
The degeneracy is lifted
IMPORTANT OBSERVATION
Structure of the Hα line of hydrogen and term scheme including the fine
structure. The expected optical spectrum is shown below (ignoring the line
widths). Darker lines indicate higher intensity. The wavenumbers are in cm-1.
Lamb Shift Experiment

A beam of H atoms is excited to the metastable 2S1/2 state by

bombardment with electrons. The beam passes through a resonator. If
electromagnetic transitions are induced there, the number of excited
atoms reaching the tungsten foil receiver is lower, and the measured
electron current correspondingly drops. The magnetic field B serves to
create an additional energetic separation between the S1/2 and the P1/2
states. This prevents mixing of those states and thereby avoids an
immediate decay via the 2P1/2 state
Above: Structure of Hα line of the hydrogen atom at room temperature. The
linewidth and thus the spectral resolution is determined by the Doppler width.
Below: The method of Doppler-free spectroscopy allows resolution of the
individual components of the Hα line.