Section 2

Atomic Spectra
(Lectures 2-3ish)
Atomic Structure:
IC yr 1
Quantum theory
of atoms / molecules
Previously:
H-Atom:
Wavefunctions, quantum numbers and energy levels
Spectral transitions: Rydberg series and selection rules
Spin and spin-orbit coupling
Alkali Metal Atoms (e.g., Na):
Penetration and shielding, quantum defects
Larger spin-orbit coupling
He Atom
Singlets and triplets
Electron correlation
General
Russell-Saunders and j-j coupling
Atoms in external fields
Lecture 2: Atomic Spectroscopy
Solutions: +
n,l,m
(r, q, j) = R
n,l
(r)Y
l,m
(, u)
2.1 Revision: The H-atom (& other 1e
-
atoms)
2
2

V + + = + (
(

2
2 2
2
2
1 1
A +
c
c
= V
r
r
r r
u
u
u u u c
c
c
c
+
c
c
= A sin
sin
1
sin
1
2
2
2
2
2
0
tc
=
Quantum numbers:
Principal quantum number, n
Orbital angular momentum quantum number, l
Orbital angular momentum projection quantum number, m
l
Permitted values:
n = 1, 2, 3,...
l = 0, 1, 2, 3, 4,... n-1
m
l
= -l, -l + 1,... +l
e.g., n = 3: l = 0: m
l
= 0 one of 3s orbital
l = 1: m
l
= 0, 1 three of 3p orbitals
l = 2: m
l
= 0, 1, 2 five of 3d orbitals
Spherical harmonics (complex)
Laguerre functions
(or magnetic)
2.1.1 Atomic Quantum Numbers
The principal quantum number, n:
determines the energies of orbitals:
n.b., E
ns
= E
np
= E
nd
...
Ionization
potential
2
2
y

=
Leads to radial wavefunctions / distribution functions:
and the mean radius
2
2
0
0 0 4
e
tc
= =

1s
2s
2p
1s
2s
2p
y y
2
P(r)
y(r) has n - l -1 nodes
4
1 1
3 2
0
y

c

= =

2.1.1 Atomic Quantum Numbers

Orbital angular momentum quantum number, l
& orb. ang. mom. projection (or magnetic) quantum number, m
l
The magnitude of the angular momentum come from l:
|l| = {l(l+1)}
1/2
and the projection of l on the z-axis is provided by m
l
:
l
z
= m
l

Lead to the angular wavefunctions and shapes of orbitals (1e

-
wavefunctions):
l
l
z
1s
2s
np
nd
(n.b. Real linear combinations plotted)
2.2 H-Atom Spectrum: Grotrian Diagrams
absorption
emission
Selection Rules:
Dn unrestricted
Dl = 1 (Laporte)
Dm
l
= 0, 1
2
2 2
1 2
y
v
| |
A
= =
|
|
\ .
Transitions observed
at wavenumbers:
Multiple series of lines (different n
1
)
Graph of n vs 1/n
2
is straight with
intercept = ionization energy
UV IR
2. 3 Origin of selection rules I
Selection Rules:
Dn unrestricted
Dl = 1
Dm
l
= 0, 1
A physical picture: Conservation of momentum
The photon has intrinsic angular momentum of
ph
= l
Total angular momentum must be conserved
in the absorption/ emission process
F I
= + l l
But |l
F
| is also quantised,
only specific relative orientations are permitted
( )
F F F
= + l l l
It is easily shown that the maximum and minimum
l
F
are given by
F max I
F min I
= + A
= A
l l i.e. l
l l i.e. l
I

F
I
I
F

F
A = + l A = l
Which is not quite our selection rule...
vectorially:
An atomic orbital with quantum number l has parity (-1)
l
Since i changes the parity, y
F
and y
I
must have opposite parity
Hence Dl 0 for reasons of symmetry
Dm
l
= 0, 1 arises due to the helicity (s = 1) of the photon
2.3 Origin of selection rules II
Selection Rules:
Dn unrestricted
Dl = 1
Dm
l
= 0, 1
All dipole allowed selection rules ultimately originate
from the need for a non-zero transition dipole moment:
F I F I
t
-
= =
}
i i
i
=

To be non-zero the integrand must be totally symmetric under the symmetry

operations of the group (the full rotation group, R
3
for atoms).
Consider the operation i:
2.5 More than one electron
For any atom other than the H-atom, the Schrdinger equation becomes:
The total energy, E, is the energy of all electrons and all interactions
The electron repulsion term, V
ij
, renders the Schrdinger equation insoluble.
For one electron: y =y(x, y, z)y
spin
= y(x, y, z, m
s
)
For two electrons: y =y(x
1
, y
1
, z
1
, (m
s
)
1
, x
2
, y
2
, z
2
, (m
s
)
2
)
In general we need: 3N spatial and N spin coordinates
Electron K.E
Nuclear attractions
Electron repulsions
2
2
i iN ij
i i i j
e

=
(

V + + =
(

2
0
iN
i
tc

=
2
0
ij
i j
tc
=

The wavefunction, y:
2.6 The orbital approximation
In order to proceed, assume Y
space
is the product of n, one-electron wavefunctions
(or orbitals)
Y
space
= j
a
(r
1
)j
b
(r
2
)j
c
(r
3
)j
d
(r
4
)... j
z
(r
n
)
For each orbital
i.e.., electron i experiences the mean field of all other electrons
Solve using numerically by e.g., Self Consistent Field approach (Hartree) to
yield orbital energies. Including exchange yields Hartree-Fock orbitals.
This method is flawed because in order to satisfy the Pauli principle we must really
write Y
space
as linear combinations of orbitals with defined symmetry with respect to
electron permutation.
Oh, and it also neglects spin and correlation (see 2.18, 2.19). But apart from that.....
2
2
i iN ij i i
i j
e

=
(

V + + =
(

e
-
e
-
repulsion averaged over
positions of all other electrons
2.7 The spectra of alkali metal atoms
Ground state electron configurations [RG] ns
1
i.e., closed shell cores
We are only interested here in valence excitations (core excitations at higher energies).
Within the orbital approximation only one electron can change orbital per photon.
Energy Levels: The effects of penetration and shielding
3p
3s
Consider the radial distribution
functions of 3s, 3p
A 3s electron spends more of its time
penetrating the core region and
experiencing the full nuclear attraction
(or equivalently, 3p is more shielded)
3s
3p
3d
Na atom
n = 3
H atom
The Energy of a level now depends on n
and l quantum numbers with E
ns
< E
np
< E
nd
2.8 The spectrum of the Na atom
2
S
2
P
2
D
2
F
H-Atom
energy
levels
sharp
series
principal
series
diffuse
series
fundamental
series
We account for penetration, shielding
with a quantum defect, d
nl
for each level:
( )
2 2 2
2 2 2
y y eff y
nl
nl
nl
o
= = =

Absorption: 3s np
Emission: ns np sharp
np ns principal
nd np diffuse
nf nd fundamental
Selection Rules:
Dn unrestricted
Dl = 1
Dm
l
= 0, 1
Dj = 0, 1
For a given l, d
nl
is only weakly
dependent on n
2.9 Spin-Orbit Coupling I
A minor effect for the H-atom SOC becomes increasingly important with atomic number
The electron has spin quantum number s =
and spin projection quantum number m
s
=
Associated with any angular momentum of a charged particle is a magnetic moment
via which orbital and spin angular momenta interact leading to spectral fine structure.
The orbital angular momentum l has (if l > 0) an associated magnetic moment to
which the spin angular momentum s can couple, yielding a total angular momentum, j.
Vectorially:
The permitted range of quantum numbers, j, are given
by a Clebsch-Gordon series:
j = l+s, l+s-1, l+s-2,....... |ls|
Hence, for a single electron, j = l :
= + j
2.9.1 Spin-Orbit Coupling II: Quantitative
The spin-orbit Hamiltonian,
But
SO

2 2
2 2
= + = + = + + j l j l l l
Hence:
( )
2 2
2
= l l
Substituting for eigenvalues:
( )
= + + + l l l
The energy of a given |l, s, j> level is
( )
l ,s , j
= + + + l l
Where A is the spin-orbit coupling constant which, for
one electron atoms is given by
( )( )
2 4
3
1
2
o
=
+ +
n.b. spin-orbit coupling
increases rapidly with
atomic number
Spin-Orbit Coupling constants:
H(2p) = 0.243 cm
-1
H(3p) = 0.072 cm
-1
Li(2p) = 0.3 cm
-1
Na(3p) = 17.2 cm
-1
K(4p) = 57.7 cm
-1
Rb(5p) = 237.6 cm
-1
Cs(6p) = 554.1cm
-1
2.10 Spectral Fine Structure
Spin-orbit coupling gives rise to splittings in spectra called fine structure .
l = 1, s =
j = 3/2
j = 1/2
m
j
= 1/2, 3/2
m
j
= 1/2
Selection Rule Dj = 0, 1 (but not 0 0) arises from conservation of angular
momentum.
e.g.,
Na D-lines
3p
3s
2
P
3/2
2
P
1/2
2
S
1/2
17 cm
-1
e.g.,2
4d
3p
Na
Na
2
P
3/2
2
P
1/2
2
D
5/2
2
D
3/2
2.11 Atomic Term Symbols
Just a succint notation for the angular momentum coupling in an atom
Term symbols contain 3 pieces of information:
2
3/2
Spin multiplicity
= 2S+1
(Where S is the total spin
quantum number for the atom)
Gives L, the total orbital angular
momentum quantum number
for the atom:
S: L = 0
P: L = 1
D: L = 2
F: L = 3, etc.
J, the total angular
momentum quantum
number for the atom.
i.e., how L and S are
coupled
2.12 Atomic Term Symbols: one unpaired electron
For atoms with a single unpaired electron:
A. s = and therefore S =
2S+1 = 2 and all terms are doublets
B. l ( and therefore L) is dependent on the orbital the electron is in:
l = 0(s), 1(p), 2(d), give rise to S, P and D terms, respectively
C. As weve seen, J depends on how L and S are coupled but the possible
quantum numbers are given by the Clebsch-Gordan series:
J = L+S, L+S-1, L+S-2,... |L-S|
e.g., So, the [Ne]3s
1
ground state configuration of Na is
2
S
1/2
The excited [Ne]3p
1
confguration yields
2
P
3/2
and
2
P
1/2
terms.
n.b., In the absence of external fields, each J level
has (2J+1) degeneracy arising from m
J
states:
1/2
-1/2
3/2
-3/2
m
J
2.13 Atomic Term Symbols: General Russell-Saunders Coupling
Term symbols really become useful when dealing with many-electron atoms.
In Russell-Saunders Coupling:
A. The spins of all electrons, s
i
couple to yield a total spin angular momentum S.
The possible values of the corresponding S quantum number arise from a
Clebsch-Gordan Series.
S = s
1
+ s
2
, s
1
+ s
2
-1,..... |s
1
s
2
| for two electrons
B. The orbital angular momenta of all electrons, l
i
couple similarly to yield a total
orbital angular momentum L.
The possible values of the corresponding L quantum number arise from a
Clebsch-Gordan Series.
L = l
1
+ l
2
, l
1
+ l
2
-1,..... |l
1
l
2
| for two electrons
e.g., coupling of orbital
angular momenta l = 1,2:
e.g., coupling of two
electron spins to give S=0, 1
2.13 Atomic Term Symbols: General Russell-Saunders Coupling
C. L and S can then couple to yield the total angular momentum, J
The possible values of the corresponding J quantum number arise from a
Clebsch-Gordan Series.
J = L+S, L+S-1,..... |L-S|
n.b., the above coupling scheme is appropriate in the limit of weak spin-orbit
coupling (small Z) and is known as Russell-Saunders Coupling
L
L
L
S
S
S
J
J
J
e.g.,
3
D terms
L = 2, S = 1
3
D
3
3
D
2
3
D
1
2.14 The spectrum of the He atom
The simplest example of a 2 valence electron atom:
The ground state is simple: configuration 1s
2
, electrons spin-paired, hence a
1
S
0
term.
This satisfies the Pauli Exclusion Principle as formulated:
No two electrons may have identical quantum numbers
- Since n, l, m
l
and s are the same for both electrons they must have different m
s
. This
lies at the heart of the aufbau principle of electronic configurations.
Singly excited configurations, 1s
1
nl
1
(n > 2) are more interesting:
Now the electrons may be spin-paired (antiparallel) or spins-aligned (parallel)
These differ in their overall spin angular momentum (S = 0 and S = 1,
respectively) denoted singlet and triplet states.
Why singlet and triplet? We need to understand the Spin wavefunctions and to do
that we must consider the more general form of the Pauli Principle:
2.15 The Pauli Principle
Each electron can have either m
s
= (spin up, or a state) or m
s
= - (spin-down, b)
Four combinations can arise: a(1)a(2), b(1)b(2), a(1)b(2), a(2)b(1)
The first two are clearly symmetric with respect to exchange but the latter two are
neither symmetric, a(1)b(2) a(2)b(1), nor anti-symmetric, a(1)b(2) a(2)b(1).
Any acceptable wavefunction must be anti-symmetric with respect to
the exchange of two identical fermions and totally symmetric with
respect to the exchange of identical bosons
Applies to the total wavefunction. We will see several manifestations of this
throughout this course but for the exchange of two electrons (Fermions, s = ):
( ) ( )
+ = +
Y
tot
= Y
space
Y
spin.
Consider Y
spin
for He:
2.16 The Pauli Principle
The two electrons are, however, indistinguishable and we can take linear
combinations of these to form eigenfunctions of the S
2
and S
z
operators:
( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( )
1 1
1 2 1 2 2 1 and 1 2 1 2 2 1
2 2
, , o o | o | o o | o |
+
( (
= + =

s
+
(1,2) is clearly symmetric with respect to exchange, s
-
(1,2) anti-symmetric
So our four spin wavefunctions are: ( ) ( )
( ) ( )
( ) ( ) ( ) ( ) ( )
( ) ( ) ( ) ( ) ( )
1 2
1 2
1
1 2 1 2 2 1
2
1
1 2 1 2 2 1
2
,
,
o o
| |
o o | o |
o o | o |
+

(
= +

(
=

Of which the 1
st
three are symmetric wrt exchange and the final one anti-symmetric.
These need pairing with Y
space
to give anti-symmetric total wavefunctions Y
tot
.
2.17 Picturing spin states
SINGLET (spin paired):
Complete cancellation of s
1
,s
2
to give
S = 0, S = 0, M
s
= 0 a single arrangement
S
M
s
=0
M
s
=+1
M
s
=-1
TRIPLET: three arrangements with S = 1 [|S| = (2)
1/2
]
n.b., m
s1,
m
s2
are no longer well-defined
S
S
2.18 The Energy of Singlet and Triplet states: Electron Correlation
For states arising from the same configuration, the triplet state lies lower in energy
than the singlet. To understand why, consider the space wavefunctions:
Consider the 1s
1
2s
1
configuration: Y
space
= j
1s
(1) j
2s
(2) or j
1s
(2) j
2s
(1)
Which, again are neither symmetric nor anti-symmetric wrt exchange.
Form linear combinations of these:
( ) ( ) ( ) ( ) ( ) { }
1 2 1 2 space s s s s

+ =
Of which Y
+
is symmetric under exchange and Y
-
anti-symmetric.
As the spin wavefunctions for the triplet states are always symmetric wrt exchange
these must be paired with Y
-
. Consider exchange for Y
-
:
When r
1
= r
2
( ) ( ) ( ) ( ) ( ) { } ( )
1 2 1 2 space s s s s space


+ = = +
( ) ( )
space space

+ = + which can only be true if
( )
space

+ =
2.19 The Energy of Singlet and Triplets: Fermi Heaps & Fermi Holes
There is zero probability of finding two electrons in the same region of space if they
are described by Y
-
(and triplet states are). Conversely there is a slight maximum in
the probability of finding two electrons described by Y
+
in exactly the same place.
|Y
-
|
2
r
1
-r
2
0
0
|Y
+
|
2
r
1
-r
2
0
0
Fermi Hole
Fermi Heap
The electrons are correlated the location of each depends intimately on the other.
Triplet
Lower energy
Singlet
Higher Energy
r
1
= r
2
is maximum electron
repulsion (i.e., high energy)
The degeneracy of singlet and triplet is lifted by the electron repulsion. A more
detailed treatment (e.g., MQM) shows the energy difference to be DE = 2K where K
is the exchange integral:
( ) ( ) ( ) ( )
2
1 2 1 2
0 12
s s s s

tc
=
2.20 The Grotrian diagram of the He atom (finally)
1s3d
1
S
3
S
1
P
1
D
3
P
3
D
Singlet Triplet
1s2s
1s3s
1s3p
1s2p
1s
2
1s2s
1s3s
1s3p
1s2p
1s3d
Emission:
1s
1
ns
1
(
1
S) 1s
1
np
1
(
1
P) 1s
1
ns
1
(
3
S) 1s
1
np
1
(
3
P)
1s
1
np
1
(
1
P) 1s
1
ns
1
(
1
S) 1s
1
np
1
(
3
P) 1s
1
ns
1
(
3
S)
1s
1
np
1
(
1
P) 1s
1
nd
1
(
1
D) 1s
1
np
1
(
3
P) 1s
1
nd
1
(
3
D)
etc.,
Absorption:
1s
2
(
1
S) 1s
1
np
1
(
1
P)
Selection Rules:
Single e

changes
Dn unrestricted
Dl = 1 (= DL)
DS= 0
NEW!
Singlet Triplet
forbidden
For each configuration, every
triplet state is lower in energy
than the corresponding singlet
2.21 Configurations, Terms and Levels
A given electron configuration may give rise, within Russell-Saunders coupling, to
several Terms (different L, S combinations). These in turn are split by spin-orbit
coupling into Levels (unique J) which comprise 2J+1 degenerate quantum states (m
J
).
For example:
ns np
configuration
terms
1
P
3
P
levels
1
P
1
3
P
0
3
P
2
3
P
1
2J+1=
3
1
5
states
(12 in total)
3
0
1
-1
2
-2
J
J
z
= m
J

m
J
=
2J+1 components
(degenerate in
zero field)
Electrostatic /
Spin correlation
magnetic
Interactions:
2.22 But beware the Pauli principle......
Consider the C atom ground state, 1s
2
2s
2
2p
2
and which terms arise.
Naively: s
1
= , s
2
= and thus S = 0, 1 (i.e., singlet and triplet terms)
l
1
= 1, l
2
= 1 and thus L = 0, 1, 2 (i.e., S, P and D terms)
1 3 1 3 1 3
i.e., we expect
But think carefully about the
3
D term:
L = 2 hence it must have M
L
= 2 component which must mean m
l1
= 1 and m
l2
= 1
S = 1 hence it must have M
S
= 1 component which must mean m
s1
= and m
s2
=
But l
1
= l
2
= 1 and n
1
= n
2
= 2
These two electrons would have to have identical quantum numbers which would
violate the Pauli Exclusion Principle.
It is possible to invoke group theory to tell if a given term is allowed (MQM p238) or
we can consider all possible combinations of M
L
and M
S
2.23 Microstate tables
l
1
=l
2
=1 m
l
= -1, 0, 1 s
1
= s
2
= m
s
= - ,
m
l
1
0
-1
Sm
l
2 0 -2 1 0 1 -1 0 -1 1 0 -1 1 0 1
Sm
s
0 0 0 0 0 0 0 0 0 1 1 1 -1 -1 -1
Draw up a table of every possible combination of m
s
and m
l
permitted by Pauli
The largest value of Sm
l
= 2 which must correspond to a D term. This only occurs
with Sm
s
= 0. Hence a
1
D term with all its 5 M
L
states (M
L
= 2, 1, 0) must exist.
P
2
:
Strike 5 such states from the table:
m
l
1
0
-1
Sm
l
2 0 -2 1 0 1 -1 0 -1 1 0 -1 1 0 1
Sm
s
0 0 0 0 0 0 0 0 0 1 1 1 -1 -1 -1
2.23 Microstate tables
m
l
1
0
-1
Sm
l
2 0 -2 1 0 1 -1 0 -1 1 0 -1 1 0 1
Sm
s
0 0 0 0 0 0 0 0 0 1 1 1 -1 -1 -1
The largest remaining Sm
l
= 1 which must correspond to a P term. This occurs with
Sm
s
=0, 1, i.e., triplet terms. Hence a
3
P term with all its 9 states must exist.
m
l
1
0
-1
Sm
l
2 0 -2 1 0 1 -1 0 -1 1 0 -1 1 0 1
Sm
s
0 0 0 0 0 0 0 0 0 1 1 1 -1 -1 -1
Leaving only a
1
S term remaining. Hence a p
2
configuration gives rise to
1
D,
3
P and
1
S.
Interestingly, a p
4
configuration gives the same terms.
2.24 Energetic ordering: Hunds Rules
Friedrich Hund
1896-1997
Within Russell-Saunders (LS) Coupling, for a given configuration:
1. The term with largest S is lowest in Energy
2. For a given S the term with largest L is lowest in Energy
3. For a term with several levels:
if the sub-shell is less than half full the lowest J level is lowest in Energy
if the sub-shell is more than half full the highest J level is lowest in Energy
Strictly applies only to finding ground states of atoms.
As weve seen, the C atom ground state p
2
configuration yields
1
D,
3
P,
1
S terms.
3
P
0
,
3
P
1
,
3
P
2
Lowest energy term
(Rules 1, 2)
Lowest energy level
(Rule 3)
Assumes spin-correlation >> orbital angular mom
m
coupling >> spin-orbit coupling
2.25 LS (Russell-Saunders) versus j-j coupling
l
1
+ l
2
+ l
3
...
L
+
s
1
+ s
2
+ s
3
...
S
+
J
Russell-Saunders (LS) Coupling:
Good quantum numbers: L, S, J
Selection Rules:
Dn unrestricted
Dl = 1
DL = 0, 1
DJ = 0, 1 (not 00)
DS= 0
2.25 LS (Russell-Saunders) versus j-j coupling
But if spin-orbit coupling is strong (large Z) then the spin, s, of an electron prefers to
couple to its own orbital angular momentum, l, to give j:
Good quantum numbers:
j
i
= l
i

J = j
1
+ j
2
+..., j
1
+ j
2
+ ... -1, etc..
n.b. L, S undefined
Selection Rules:
Dn unrestricted
Dl = 1, Dj = 0, 1 for one electron
Dl = 0, Dj = 0 for other electrons
DJ = 0, 1 (not 00)
l
1
l
2
l
3
+ + +
s
1
s
2
s
3
+ + +
j
1
+ j
2
+ j
3
...
J

m
a
g
n
e
t
i
c
electrostatic
e.g., down Group IV:
C Si Ge Sn Pb
Coupling: LS intermediate j-j
j-j Coupling:
= the Bohr magneton
2.26 Atoms in External Fields: lifting degeneracy
In the absence of external fields the 3 M
L
components of an
1
P term are degenerate.
But the magnetic moment associated with the orbital angular momentum can
interact with any external B field to lift this degeneracy.
2.26.1 The Normal Zeeman Effect (when S = 0)
Classically, the interaction energy:
E = m.B = g
e
L
z
B
[ g
e
is the gyromagnetic (or magnetogyric) ratio]
0
1
-1
M
L
=
B
Hence, quantum mechanically:
E = g
e
M
L
B = m
B
M
L
B
e B e
e

= =
L
L
z
lifts the field-free degeneracy resulting in splittings in the spectrum
As weve seen S and L give rise to magnetic moments. These can interact with an
externally applied B field:
2.26.1 The Normal Zeeman Effect (when S = 0) cont.
0
1
-1
M
L
=
B
L
L
z
Selection Rule: DM
L
= 0, 1
M
L
2
-2
-1
0
1
-1
0
1
1
P
1
D
DM
L
= -1 0 1
v
B = 0 B > 0
E = m
B
M
L
B
0
1
-1
2
-2
B
M
L
=
L
2.26.2 The Anomalous Zeeman Effect (when S 0)
Of course the spin angular momentum also gives rise to a magnetic moment and
when both L and S are non-zero the splittings are more complex.
B
J
L
S
Now, E = g
e
(L + 2S).B
But we need consider only projections of L and S on B.
e.g.,
( )( )
2
=
J J
J
( )
( ) ( ) ( )
( )
1 1 1
1
2 1
J
S S L L
g L,S
+ + + +
= +
+
J J
J J
Where the Land g-factor,
n.b., when S = 0, J = L and g
J
= 1 Normal Zeeman Effect
e J e J J
= =
e.g., g
J
= 1.5 for a
3
P
2
level
= 2.00 for
3
S
1
level (normal spin g-factor)
2.26.2 The Anomalous Zeeman Effect cont.
Selection Rule: DM
J
= 0, 1
M
J
3/2
-3/2
-1/2
1/2
2
P
1/2
2
D
3/2
DM
J
= -1 0 1
v
B = 0 B > 0
-1/2
1/2
So the levels are split into 2J + 1 components but the splitting itself is dependent
on J, L, and S.
i.e., splitting proportional to m
J
, M
J
& B
E = -g
e
g
J
M
J
B