21/05/2019 LS vs.

jj coupling, Zeeman effect, and hyperfine structure :: Atomic Physics :: Rudi Winter's web space

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LS vs. jj coupling, Zeeman effect, and hyperfine

structure
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LS coupling
Beamtimes
Papers The various orientations sub-shell orbital spin total term
Teaching of orbital angular
ph215 1s 's' → l = 0 s = 1

Thermodynamics momentum and spin give 1 1

2

rise to the fine structure of 2p 'p' → l = 1 s = 1

Quantum 2 2
2
Phys.
Partial Diff.
atomic spectra. This is S = |s − s | J = |L − S| 1 2
1

Eq. known as spin-orbit L = |l − l | = 0

1
= L + S = 1
2
P 1

ph324/335/338 coupling or LS coupling combi J = |L − S| = 0 P

3
Condensed = l + l 0

Matter since the total orbital 1

S = s + s
2
1 2
3
= 1 J = |L − S| + 1 = 1 P
ph327 angular momentum, L, of = 1
1

Atomic Phys. a group of electrons J = L + S = 2 P

3
2
Fourier
Y3/4 projects interacts with the total spin, S, of that group of electrons, following the vector model of
Walking in angular momentum. We've already seen this for hydrogen and for helium. The table
Wales recapitulates the situation for an excited helium atom in the 1s 2p configuration. To
Other derive the term symbols for the different spin-orbit states, we first need to calculate the
Diversions total orbital angular momentum and total spin from those of the individual electrons,
In this section respectively (shown by column, in red). Then L and S are combined to find the total
angular momentum of this group of electrons, J (shown by row, in blue). The possible
subject index combinations for L, S and J according to the vector model are given by the Clebsch-
What is Atomic
Gordan sequences:
Physics?
Spectroscopy
Hydrogen: Wave L = |l1 − l2 | ⋯ l1 + l2 (in integer steps)
functions
S = |s1 − s2 | ⋯ s1 + s2 (in integer steps)
Perturbation theory
J = |L − S| ⋯ L + S (in integer steps)
Radiation and
matter
Fine structure
Helium The term symbols are then composed by writing the total orbital angular
Periodic table 2S+1
L
momentum, L, in spectroscopic notation (S,P,D,F,... - capitalised, since this refers
J

LS/jj, Zeeman, to the total orbital angular momentum of a group of electrons) with the total
hyperfine
angular momentum, J , as a subscript. Finally, the spin multiplicity, 2S + 1, is
Dr Rudolf Winter
calculated from the total spin and attached to the term symbol as a leading superscript.
The term symbols for all four terms in the 1s 2p configuration are shown in green in the
Materials Physics table above. In this case, there is a singlet state ( P ) and a triplet of states ( P , P ,
1
1
3
0
3
1

Aberystwyth 3
P ). In almost all cases, the spin multiplicity indicates how many states there are in
2
University
each group (see below for an exception).
Penglais
Aberystwyth
SY23 3BZ
Wales In principle, any other electron sub-shell orbital spin
configuration can be treated in
[Link]/ruw/teach/327/[Link]#jj 1/5
21/05/2019 LS vs. jj coupling, Zeeman effect, and hyperfine structure :: Atomic Physics :: Rudi Winter's web space
Ffiseg Defnyddiau exactly the same way, although the 2p 'p' → l 1 = 1 s1 =
1

Prifysgol number of different terms can

2

Aberystwyth 3p 'p' → l = 1 s2 =
1

become quite large. The two tables

2
2

Penglais
Aberystwyth to the right show a simple example L = |l1 − l2 | = 0 S = |s1 − s2 | = 0

SY23 3BZ of a configuration with two valence combi L = |l1 − l2 | + 1 = 1 S = s1 + s2 = 1

Cymru electrons, 2p 3p. L = l1 + l2 = 2

ruw@[Link]
Again, the total orbital angular
L→
momentum and the total spin are 0→'S' 1→'P' 2→'D'
S↴
calculated from those of the
Sunset today:
individual electrons. In this case, J = |L − S| J = |L − S| J = |L − S|

the Clebsch-Gordan sequence 0 = L + S = L + S = L + S

21:15
produces three possible values for
1 1 1
= 0 → S = 1 → P = 2 → D
1'27 later than 0 1 2

y'day L rather than just one. Spin-wise, J = |L − S| J = |L − S|

the situation is the same for any = 0 → P = 1 →

3
D 0
3
1
J = |L − S|
two-electron configuration since J = |L − S| + 1 J = |L − S| + 1

the spin of a single electron is 1 = L + S

3 3
= 1 → 3
P = 2 → D 1 2

always s = . We then have to look

1

2
= 1 → S
J = L + S
1
J = L + S
at all possible permutations of the = 2 → P = 3 →
3
D 2
3
3
total orbital angular momenta and
the total spin, as shown in the second table on the right. For each permutation, we
calculate the total angular momentum, J , and work out the term symbol as before.
There are three separate singlets, two proper triplets consisting of three states each, and
one additional "triplet" state, S . This is an exception to the rule that the multiplicity
3
1

indicates the number of states in a particular group of terms - the reason this "triplet"
has only one member is the fact that the Clebsch-Gordon sequence uses the magnitude
of the difference of L and S and thus |L − S| and L + S are the same in this case.

The energies of the different terms depend on the direct and exchange integrals, as we
have seen in the case of helium. In principle these can be calculated numerically for all
terms using perturbation theory. However, if all we need to know is the configuration of
the ground state, Hund's rules can predict which term is populated in the ground state
for each configuration without the need to calculate any energies: The term with the
lowest energy is the one with the highest S. If there are several of those, then the one
with the highest L will have the lowest energy. If there are still several, the lowest-
energy term will be the one with the lowest J . Therefore, from the table above, the term
at the bottom of the splitting will be D . 3
1

jj coupling
Since perturbation theory is based on making small changes to known
l1 s1 → j systems, perturbations must be applied in the correct order, i.e. in order
1

l2 s2 → j
of decreasing severity. The fine structure (exchange integral) and the
2

↓ ↓ ↓
residual electrostatic interaction are of comparable size but depend
differently on the atom number Z . The fine structure splitting increases
L S → J
with Z , while the residual electrostatic interaction rises only gradually
2

with Z . For light elements, near the top of the periodic table, H^ re

dominates and has to be applied first, but for heavier elements, this is less clear-cut, and
a transition to a different spin-orbit coupling regime, jj coupling occurs as a
consequence.

In jj coupling, the orbital angular momentum, l, and spin, s , of each electron are first
coupled to form a total angular momentum, j , for that electron. These single-electron
total angular momenta are then combined into a total angular momentum, J , for the
f l t
[Link]/ruw/teach/327/[Link]#jj
(bl l l ti th h i t i b ) Thi i i t t 2/5
21/05/2019 LS vs. jj coupling, Zeeman effect, and hyperfine structure :: Atomic Physics :: Rudi Winter's web space
group of electrons (blue calculation pathway shown in matrix above). This is in contrast
to LS coupling (red pathway), where the total orbital angular momentum, L, and total
spin, S, of the system are calculated first and then combined to the total angular
momentum, J , of the whole system.
Note: Notation: lower case for momenta of individual electrons, upper case for combined momenta.

j1 → 1
In general, the results from both coupling schemes
j2 ↴ 2 are different. For example, for the 1s 2p
1
configuration shown at the top of the page, jj
2
J = |j1 − j2 | ⋯ j1 + j2 = 0 or 1
coupling results in two doublets rather than a singlet
= 1 or 2and a triplet: For the 1s electron
3
J = |j1 − j2 | ⋯ j1 + j2
2

j = |l − s | = l + s = and for the 2p electron

1
1 1 1 1 1
2

or . These combine as shown in the table, resulting in two

1 3
j2 = |l2 − s2 | ⋯ l2 + s2 =
2 2

doublets.

Zeeman effect
The degenerate states of a sub-
shell of hydrogen, distinguished
by their magnetic orbital
angular momentum quantum
number, m , split into l

energetically distinct levels

when placed in a magnetic field
according to their orientation
relative to the field. In the same
way, spin-orbit terms split
according to their magnetic
total angular momentum quantum number, M , into 2J + 1 separate J

states. This removal of degeneracy due to interaction with a magnetic

field is known as the Zeeman effect and is mediated by the magnetic
moment of the atom. The magnetic moment μ⃗ is linked to the angular momentum (both
orbital and spin) via the Bohr magneton, μ , the "quantum of magnetisation":
B

⃗  ⃗ 
μ ⃗  = −μ B L − ge μ B S ,

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21/05/2019 LS vs. jj coupling, Zeeman effect, and hyperfine structure :: Atomic Physics :: Rudi Winter's web space
μ μB ge μ B ,

where g is the electron spin g-factor, a fundamental constant very close to the value 2.
e

Since this formula adds the electron's two angular momenta together, the magnetic
moment depends on the combined angular momentum, J ,⃗  and the Hamiltonian for the
Zeeman effect is proportional to the scalar product of the total angular momentum and
the external field, i.e. the projection of one of the vectors on the other (see diagram on
the left):
^ ⃗   ⃗ 
H Zeeman ∝ J ⋅ B .

Each level within a term, even a singlet, therefore splits into its 2J + 1 levels with
different M quantum number. As an example, the situation for a P singlet is shown
J
1
1

on the right.

Spin-orbit recap

The schematic summarises the splittings due to the spin-orbit interaction: The electron
configuration describes electrons in a combination of sub-shells, in the example shown
a two-electron system
with 3s 3p
configuration. Spin-
orbit coupling (in this
case following the LS
coupling scheme)
results in a shift and a
splitting into two
terms due to the direct
and exchange
integrals, respectively.
One of the term is a
singlet, the other a
triplet with three
associated levels
according to their
combined total
angular momentum
quantum number, J . If
placed inside a
magnetic field, the
Zeeman effect is
observed, and each level splits into 2J + 1 Zeeman states - the extent of this splitting
depends linearly on the magnitude of the magnetic field. Note that the Zeeman states
are not created by the magnetic field - they are distinct states even at B = 0, but since
they are degenerate in the absence of a field, they cannot be distinguished by
spectroscopic means. The diagram is not to scale - the strength of the exchange
interaction is of the order of 1eV, the fine-structure levels are of the order of 10-5eV
apart (GHz range), and the Zeeman splitting is of the order of 10-10eV (kHz range).

Hyperfine structure
There is a further splitting below the spin-orbit related spectral detail,
aptly called hyperfine interaction. It is due to the interaction between
the nuclear spin, I ,⃗  and the combined total angular momentum, J ,⃗ 
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21/05/2019 LS vs. jj coupling, Zeeman effect, and hyperfine structure :: Atomic Physics :: Rudi Winter's web space
p , , g , ,
and effectively adds another angular momentum to the vector model.
Nuclear spins are the combined spins of all the protons and neutrons
in the nucleus and vary between isotopes of the same element. Since
nuclei are much heavier than electrons, their spin is much smaller in
magnitude than that of an electron, and the nuclear spin quantum
number can be zero, integer or half-integer.

The magnetic moment associated with the nuclear spin, μ⃗  , aligns in I

the magnetic field, B⃗  , induced by the moving electrons. As a result,

el

the nuclear spin plays the same role in the hyperfine interaction as the
magnetic field does in the Zeeman effect: The perturbation Hamiltonian is again
proportional to the scalar product of the two vectors:
^ ⃗  ⃗   ⃗ 
H hfs = −μ ⃗  Bel ∝ I ⋅ J .
I

The hyperfine interaction is of a strength comparable to that of the Zeeman effect at

very low magnetic fields. Its states are distinguished by the quantum number F , which
is derived from the possible orientations of J ⃗ relative to I ⃗ using the vector model of
angular momentum in the same way as J arises from the relative orientation of L⃗  and S .⃗ 
Naturally, an atom with a nuclear spin of zero does not show any hyperfine structure
splitting, and the hyperfine interaction is strongest for s-electrons due to their non-zero
probability density inside the nucleus - this is known as the Fermi contact interaction.

Conclusion
That concludes this overview of atomic physics. We have used the Schrödinger
equation to calculate the states of the hydrogen atom and their energies. Using
perturbation theory in order of diminishing severity, we have added layers of
complexity to the structure of the atom. As a result, a series of splittings of previously
degenerate energy levels arises. We have used the vector model of angular momentum
to understand how spin and orbital angular momentum couple and how the structure of
complex atoms is affected by this. We have encountered spectroscopy as a means to
measure the electronic structure of an atom by observing absorption and emission
events between different states.

Dr Rudolf Winter
Department of Physics, Aberystwyth University, Penglais, Aberystwyth SY23 3BZ, Wales
Adran Ffiseg, Prifysgol Aberystwyth, Penglais, Aberystwyth SY23 3BZ, Cymru
ruw@[Link]

Blame me, not my employer etc. etc.

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