Atoms in Magnetic Field

Zeeman and Paschen Back Effects

Zeeman Effect

• We will discuss the effect of static magnetic field on the

spectral lines.
• The effect is known as Zeeman effect and the pattern seen
after applying the magnetic field is known as Zeeman
pattern.
• We will also discuss the Normal and Anomalous Zeeman
effect.
• We will see also the change of the Zeeman pattern when
the magnetic field is increased, i.e., Paschen Back effect.
 Normal Zeeman effect

o Observed in atoms with no spin.

N

o Total spin of an N-electron atom is Sˆ   sˆi

i1

o Filled shells have no net spin, so only consider valence electrons. Since electrons
have spin 1/2, not possible to obtain S = 0 from atoms with odd number of valence
electrons. 
o Even number of electrons can produce S = 0 state (e.g., for two valence electrons, S
= 0 or 1).
o All ground states of Group II (divalent atoms) have ns2 configurations => always
have S = 0 as two electrons align with their spins antiparallel.
o Magnetic moment of an atom with no spin will be due entirely to orbital motion:
B ˆ

ˆ  L


 Norman Zeeman effect

o Interaction energy between magnetic moment and a uniform magnetic field

is:
ˆ  Bˆ
E  

0 
o Assume B is only in the z-direction:  
 Bˆ  0 
 
Bz 

o The interaction energy of the atom is therefore, E  z Bz  B Bz ml


where ml is the orbital magnetic quantum number. This equation implies
that B splits the degeneracy of the ml states
 evenly.
 Norman Zeeman effect transitions

o But what transitions occur? Must consider selections rules for ml: ml = 0,
±1.
o Consider transitions between two Zeeman-split atomic levels. Allowed
transition frequencies are therefore,
h  h 0  B Bz ml  1
h  h 0 ml  0
h  h 0  B Bz ml  1
o Emitted photons also have a polarization, depending
on which transition 
they result from.

 Norman Zeeman effect transitions

o Longitudinal Zeeman effect: Observing along magnetic field, photons must

propagate in z-direction.

o Light waves are transverse, and so only x and y polarizations are possible.

o The z-component (ml = 0) is therefore absent and only observe ml = ± 1.

o Termed -components and are circularly polarized.

o Transverse Zeeman effect: When observed at right angles to the field, all three
lines are present.

o ml = 0 are linearly polarized || to the field.

o ml = ±1 transitions are linearly polarized at right angles to field.

 Norman Zeeman effect transitions

o Last two columns of table below refer to the

polarizations observed in the longitudinal and
transverse directions.
o The direction of circular polarization in the
longitudinal observations is defined relative to B.
o Interpretation proposed by Lorentz (1896).

-  +
(ml=-1 ) (ml=0 ) (ml=+1 )
 Anomalous Zeeman effect

o Discovered by Thomas Preston in Dublin in 1897.

o Occurs in atoms with non-zero spin => atoms with odd number of
electrons.

o In LS-coupling, the spin-orbit interaction couples the spin and orbital

angular momenta to give a total angular momentum according to

Jˆ  Lˆ  Sˆ
o In an applied B-field, J precesses about B at the Larmor
frequency.

o L and S precess more rapidly about J to due to spin-orbit
interaction. Spin-orbit effect therefore stronger.
 Anomalous Zeeman effect

o Interaction energy of atom is equal to sum of interactions of spin and orbital

magnetic moments with B-field:
E  z Bz
 (zorbital  zspin )Bz

 Lˆ z  gsSˆ z B Bz

where gs= 2, and the < … > is the expectation value. The normal Zeeman effect is
obtained by setting Sˆz  0 and Lˆ z  ml .

o In the case of precessing atomic magnetic in figure on last slide, neither Sz nor Lz
 Only Jˆ  m
are constant. is well defined.
z j

o Must therefore project L and S onto J and project onto

z-axis =>  ˆ ˆ
J J B
ˆ   | Lˆ | cos1
  2 | Sˆ | cos 2
ˆ
|J | ˆ
|J |
 Anomalous Zeeman effect

o The angles 1 and 2 can be calculated from the scalar products of the respective vectors:
Lˆ  Jˆ | L || J | cos 1
Sˆ  Jˆ | S || J | cos 2

Lˆ  Jˆ Sˆ  Jˆ B ˆ
which implies that 
ˆ   2 J (1)
| Jˆ |2 | Jˆ |2

o Now, using Sˆ  Jˆ  Lˆ implies that Sˆ  Sˆ  (Jˆ  Lˆ )  (Jˆ  Lˆ )  Jˆ  Jˆ  Lˆ  Lˆ  2Lˆ  Jˆ


therefore Lˆ  Jˆ  (Jˆ  Jˆ  Lˆ  Lˆ  Sˆ  Sˆ ) /2
 
Lˆ  Jˆ

 j( j  1)  l(l  1)  s(s  1) 2
/2
so that
| Jˆ |2 j( j  1) 2


 j( j  1)  l(l  1)  s(s  1)
2 j( j  1)
Sˆ  Jˆ

 j( j  1)  s(s  1)  l(l  1)
o Similarly, Sˆ  Jˆ  (Jˆ  Jˆ  Sˆ  Sˆ  Lˆ  Lˆ ) /2 and | Jˆ |2 2 j( j  1)



 Anomalous Zeeman effect

o We can therefore write Eqn. 1 as

 j( j  1)  l(l  1)  s(s  1)  j( j  1)  s(s  1)  l(l  1)B ˆ
 
ˆ 2  J
 2 j( j  1) 2 j( j  1) 

B ˆ
o This can be written in the form 
ˆ  g j J

j( j  1)  s(s  1)  l(l  1)
where gJ is the Lande g-factor given by g j  1
2 j( j  1)


o This implies that z  g j B m j

and hence the interaction energy with the B-field is
E  z Bz  g j B Bz m j
o Classical 
theory predicts that gj = 1. Departure from this due to spin in
quantum picture.

 Anomalous Zeeman effect spectra

o Spectra can be understood by applying the selection rules for J and mj:

j  0,1
m j  0,1

o Polarizations of the transitions follow the

same patterns as for normal Zeeman effect.

o For example, consider the Na D-lines
at right produced by 3p  3s transition.
D1-line
D2-line
Triplet to triplet transition (3S1 →3P1 )
 Transition 1D2 →1P1

1D
2

1P
1
 Strong field case: Paschen-Back effect

o Zeeman effect is splitting of spectral lines in "weak" magnetic fields.

o "Weak" means that the splitting of energy levels in the magnetic field is
small compared to fine structure splitting;
o This means, the spin-orbit coupling is stronger than the coupling of either the
spin or the orbital moment alone to the external magnetic field.
o Since spin-orbit coupling increases rapidly with increasing nuclear charge Z,
the conditions for a "strong" field are met at a much lower field with light
atoms than with heavy atoms.
o For example, the spin-orbit splitting of the sodium D lines is 17.2 cm-1 while
the splitting for the corresponding lines of the lithium atom is 0.3 cm-1 .
o The Zeeman splitting in an external field B0 of 30 kG (3 T) is the same in
both cases, about 1 cm-1 .
o Thus this field is a "strong“ magnetic field for lithium, but a "weak" field for
sodium.
 Strong field case: Paschen-Back effect
When the magnetic field Bz is strong
enough so that the above condition is no
longer fulfilled, the splitting picture is
simplified.
The magnetic field dissolves the fine
structure coupling.
l and s are, to a first approximation,
uncoupled, and precess independently
around Bz
The quantum number for the total angular
momentum, j, thus loses its meaning.
This limiting case is called the Paschen-
Back effect.
The components of the orbital and spin moments 𝜇𝑙 𝑧 and 𝜇𝑠 𝑧 in the field direction
are now individually quantised. The corresponding magnetic energy is
𝑉𝑚𝑙 ,𝑚𝑠 = 𝑚𝑙 + 2𝑚𝑠 𝜇𝐵 𝐵𝑧
and the splitting of the spectral lines is ∆𝐸 = ∆𝑚𝑙 + 2∆𝑚𝑠 𝜇𝐵 𝐵𝑧
Selection rules