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6. Zeeman Effect
The Zeeman effect is the modification of an atomic spectrum by the application of a strong
magnetic field. It arises from the interaction between applied magnetic fields and the magnetic
moments due to orbital and spin angular momentum.
The interaction between the atoms and the field can be classified into two regimes:
 Weak fields: the Zeeman effect, either normal or anomalous;
 Strong fields: the Paschen-Back effect.
Polarization of emitted photon: The polarization of photons emitted in the direction of a

ks
magnetic field, or at right angle to magnetic field is different and these polarizations are shown
below:
(i) Longitudinal observation: When the emitted photons are seen in the direction of magnetic
field than the π line is found to absent, only ± are presents & both ± are circularly polarized.

K K
BZ
 Left hand Right hand
circularly circularly
 polarised
polarised

zi


  line   line
Magnetic field

(ii) Transverse observation: When the emitted photons are seen in the perpendicular direction of
magnetic field than all three π, ± are found to be present and they all are linearly polarized.
B2 z z
:
E
fi
o y o y
Magnetic field
x K x K
E

  ,   lines, with   line, with K & E

  along - ve z - axis
K & E in xy plane

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6.1 Normal Zeeman Effect:

The normal Zeeman effect is observed in atoms with no spin. The total spin of an N-electron atom
is given by:
N
S   si
i 1

Since all the individual electrons have spin 1/2, it will not be possible to obtain S = 0 from atoms
with an odd number of valence electrons. However, if there is an even number of valence
electrons, we can obtain S = 0 states.

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 It is shown by singlet (2S + 1 = 1) spectral line i.e. S = 0
 Singlet spectral line viewed normal to the field is split into three plane polarized
components. A central unshifted line with E-vector vibrating parallel to the field (π-
component) & two other lines equally displaced one on either sides with E-vector
perpendicular to B – field (σ- component)
Splitting in Normal Zeeman Effect:
The magnetic moment of an atom with no spin will originate entirely from its orbital motion:
  
l   B L

zi
In the presence of weak applied field, the magnetic moment precesses around the field with
Larmor frequency.

L e
Larmor frequency:   B  B
L 2m
The interaction energy between a magnetic dipole moment and a uniform magnetic field B is
given by the dot product of magnetic moment and applied field
 
fi
E    l .B
If we set up the axes of our spherically-symmetric atom so that the z axis coincides with the
direction of the field, than the interaction energy is
E    z Bz   B Bz M L
eh
  M L
4 m

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Example: 1D2 – 1P1 : L=2&L=1

- In weak B – field, line breaks into 2L + 1 = 5 & 3 equivalent components
- For L = 2 : ML = 2, 1, 0, -1, -2
For L = 2 : ML = 0, 1, 0, -1

+2

1 +1
D2
0

ks
-1

-2
E = h h

1 +1
P1
0

-1

 
zi
No Field In Field

- Selection Rule: ∆ML = 0, ±1

- Separation of Zeeman Components
e
  1 –  0   2 –  3 
4 m
fi
c 
Since v   v  c
 2
2
v  v
c
c 2
  
4 m

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6.2 Anomalous Zeeman Effect:

The anomalous Zeeman effect is observed in atoms with non-zero spin. This will include all
atoms with an odd number of electrons i.e. it is shown by multiplet spectral lines (S ≠ 0)

Splitting in Anomalous Zeeman Effect:

- Explain by considering ‘SPIN’ of the electron B
 
L e S e
-   Where   2
L 2m S 2m
S

ks
Because of inequality of two radius
   
the total    L   S is not exactly antiparallel to J J
   
μJ = Component of  L along J + Component of  S along J

e  L
J  g J
2m
J ( J  1)  S (S  1)  L( L  1) L
Where, g  1  :
2J ( J  1)
J
Is the Lande’s g-factor
zi

J e S
- Larmor frequencies: w   g 
J 2m
eh
- Energy of precession:   wJ Z  gM J 
4 m
- J-level split into (2J + 1) Zeeman levels
- Relative spacing of the Zeeman levels of one term and those of another are different and
determined by g – factor alone.
fi
The polarizations of the transitions follow the same patterns as for the normal Zeeman effect:
 With longitudinal observation the MJ = 0 transitions are absent and the MJ = ±1
transitions are ± circularly polarized.
 With transverse observation the MJ = 0 transitions are linearly polarized along the z
axis (i.e. parallel to B) and the MJ = ±1 transitions are linearly polarized in the x-y plane
(i.e. perpendicular to B).

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Example: Sodium D line i.e. Zeeman Splitting of D1 & D2 of Na:

The sodium D lines correspond to the 3p → 3s transition. At B = 0, the spin-orbit interaction
2
splits the upper 3p P term into the 2P3/2 and 2P1/2 levels separated by 17 cm-1. The lower 2S1/2
level has no spin-orbit interaction.
The splitting of the lines in the field is shown schematically in Fig.
2 2 2 2
P1/2 → S1/2 and P3/2 → S1/2
MJ

+3/2
+1/2

ks
2
P3/2
- 1/2

-3/2

2
P1/2 +1/2

-1/2

D1 D2
zi
2 +1/2
S1/2

-1/2




No Field 

fi
In Field

The 2P3/2 level splits into four MJ states, while the two J = 1/2 levels each split into two states.
The splittings are different for each level because of the different Lande g-factors. On applying
the MJ = 0; ±1 selection rule, we find four allowed transitions for the D1 line and six for the D2.
These transitions are are shown in above figure.

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Selection Rule: ∆MJ = 0, ± 1 (MJ = 0 ↔ MJ = 0 if ∆J = 0)

Note: In the normal Zeeman effect we observe three lines with an energy spacing equal to
In the anomalous effect, there are more than three lines, and the spacing is different to the
classical value: in fact, the lines are not evenly spaced.

Intensity of D1 and D2 Lines: The intensity of light depends on the number of atoms falling to
ground state. The degeneracy factor (2J+1) decide the population in Jth state, therefore the
intensity ratio of D2 and D1 is

ks
3
I D2 2J2 1 2  2 1 2
  
I D1 2 J1  1 2  1  1 1
2
6.3 Paschen-Back Effect
The Paschen-Back effect is observed at very strong magnetic fields. The criterion for observing
the Paschen-Back effect is that the interaction with the external magnetic field should be much
stronger than the spin-orbit interaction:
(1) When the strength of B-field is increased, the separation between Zeeman components
increases until they become greater than the separation between multiplet fine structure
zi
components. The Anomalous Zeeman pattern than changes over to Normal Zeeman pattern.
This phenomenon is known as Paschen – Back Effect.
 
(2) In extremely high B, coupling between J & B exceeds than between L & S . Precession of J
  
about B becomes faster than L & S about J . Coupling between L & S is partially broken
   
down & J is no longer fixed in magnitude i.e. L & S precess independently about  with

Larmor frequency.
fi
The z-components of orbital angular and spin angular momentum is Lz = MLħ & Sz = msħ
(3) The precession frequency or Larmor frequency is
eB eB
L  and  S  2
2m 2m
(4) Energy of the Precession is
eB
EL  L Lz  M L
2m

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eB
ES  S S z  2 M L
2m
The main energy shift ∆E = ∆EL + ∆ES
eh
    L  2 S  
4 m
(5) Splitting gives (2L + 1) (2S + 1) level.

2
Example: P → 2S i.e. 2P1/2,3/2 → 2S1/2 of Na doublet

ks
Terms (2L + 1) (2S + 1) ML MS Shift = ML + 2MS
2
P 1 1/2, -1/2 2, 0
L = 1, S = 1/2 6 0 1/2, -1/2 1, -1
-1 1/2, -1/2 0, -2
2
S
L = 0, S = 1/2 2 0 1/2, -1/2 1, -1

Selection Rule: ∆ML = 0, ± 1 and ∆MS = 0

zi
fi

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