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In year 1896 Pieter Zeeman discovered when a sodium flame is placed between the poles of a
powerful electromagnet the two lines of the first principal doublet are considerably broadened.
Lorentz pointed out that this phenomenon is in harmony with the electron theory of matter and
radiation proposed by himself. He predicted from the theoretical considerations that the light
from these lines should be polarized by the magnetic field, circularly polarized if viewed in a
direction parallel to the lines of force, and plane polarized if viewed at right angles to the field.
These predictions were later verified by Zeeman using Nicol prisms as analyzers. Later the
broadening was found to be a distinct splitting of spectral lines into as many as 15 components.
Zeemans discovery earned him the 1902 Nobel Prize for Physics,
which he shared with a former teacher, Hendrik Antoon
Lorentz, another Dutch physicist. Lorentz, who had earlier developed
a theory concerning the effect of magnetism on light, hypothesized
that the oscillations of electrons inside an atom produce light and
that a magnetic field would affect the oscillations and thereby the
frequency of the light emitted. This theory was confirmed by
Zeemans research and later modified by quantum mechanics,
according to which spectral lines of light are emitted when electrons
change from one discrete energy level to another. Each of the levels,
characterized by an angular momentum (quantity related to mass
and spin), is split in a magnetic field into substates of equal energy.
These substates of energy are revealed by the resulting patterns of
spectral line components.
When a light source is brought into a magnetic
field, each emitted spectral line is split into a
number of components. To a first approximation,
the splitting is proportional to the strength of the
magnetic field. This is called Zeeman effect.
NOMENCLATURE : Historically, one distinguishes between the normal(observed when net spin quantum number of atom is
0) and an anomalous Zeeman effect (discovered by Thomas Preston in Dublin, Ireland in 1897). The anomalous effect appears
on transitions where the net spin of the electrons is an odd half-integer, so that the number of Zeeman sub-levels is even. It
was called "anomalous" because the electron spin had not yet been discovered, and so there was no good explanation for it at
the time that Zeeman observed the effect.

Thomas Preston (1860 in Kilmore, County Armagh 1900 was an Irish scientist whose research was concerned with
heat, magnetism, and spectroscopy. He established empirical rules for the analysis of spectral lines, which remain associated
with his name. In 1897 he discovered the Anomalous Zeeman Effect, a phenomenon noted when the spectral lines of elements
were studied in the presence or absence of a magnetic field.
He was educated at The Royal School, Armagh, the Royal University of Ireland and Trinity College, Dublin. From 1891 to 1900 he
was Professor of Natural Philosophy at University College Dublin. He was a Fellow of the Royal University of Ireland and of
the Royal Society, London and was a distinguished spectroscopist. His two major textbooks remained in continuous use for over
What causes this splitting?
The splitting of the lines is evidently due to a splitting of the terms in the magnetic
field. The influence of a magnetic field on energy levels is, perhaps, most clearly
understood by considering how a magnetic needle behaves in a magnetic field. The
potential energy of the magnetic needle depends upon its direction with respect to
the magnetic field. Therefore, if the needle is displaced from the direction of the
field and then released, it will vibrate back and forth about its equilibrium position
(the position of minimum potential energy that is, when the needle is in the
direction of the field) and can be brought to rest only by the dissipation of its
energy. Like the magnetic needle, the atom generally has a magnetic moment y. The
rotation of electric charges which, even according to wave mechanics, takes place in
the atom always leads to the production of a magnetic moment in the direction of
the axis of rotation. This effect follows the same laws that operate when a current
flows through a wire ring (circular electric current). The greater the angular
momentum of the atom, the greater will be the magnetic moment. Because of the
inherent connection between magnetic moment and angular momentum, we have
to take into account the gyroscopic forces when we discuss the behavior of an atom
in a magnetic field. The effect of these gyroscopic forces is that the rotational axis of
the atom (direction of y) does not vibrate back and forth about the position of
minimum energy, but executes a precessional motion with uniform velocity about
the direction of the field (so-called Larmor precession). This leads to slight change
in energy of an atom from energy in field free space. Thus in a sample consisting of
large number of atoms we have splitting of level (single in absence of field) into a
number of components. The number of levels split have been calculated to be 2J+1
in number.(in case of normal Zeeman effect where s=0 so that j=l we have 2l+1
components of a level.
o Observed in atoms with no spin.

o Total spin of an N-electron atom is

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
An external magnetic field will exert a torque on a magnetic dipole and the magnetic potential
energy which results is

The magnetic dipole moment associated with the orbital angular momentum is given by

For magnetic field in the z-direction this gives

Considering the quantization of angular momentum , this gives equally spaced energy levels
displaced from the zero field level by

This displacement of the energy levels gives the uniformly spaced multiplet splitting of the
spectral lines which is called the normal Zeeman effect.
While the Zeeman effect in some atoms (e.g., hydrogen) showed the expected equally-
spaced triplet, in other atoms the magnetic field split the lines into four, six, or even
more lines and some triplets showed wider spacing than expected. These deviations
were labeled the "anomalous Zeeman effect" and were very puzzling to early
researchers. The explanation of these different patterns of splitting gave additional
insight into the effects of electron spin. With the inclusion of electron spin in the total
angular momentum, the other types of multiplets formed part of a consistent picture.
So what has been historically called the "anomalous" Zeeman effect is really the
normal Zeeman effect when electron spin is included.

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

o In an applied B-field, J precesses about B at the Larmor


o L and S precess more rapidly about J to due to spin-orbit

interaction. Spin-orbit effect therefore stronger.
As stated above, the anomalous Zeeman effect occurs when the spin of either the initial or
the final states, or both, is nonzero. The calculation of the energy-level splitting is
complicated a bit by the fact that the magnetic moment due to spin is 1 rather than 1/2
Bohr magneton, and as a result the total magnetic moment is not parallel to the total
angular momentum. Consider an atom with orbital angular momentum L and spin S. Its total
angular momentum is
whereas the total magnetic moment is
= -(glBL +gsBS )2
Since gl = 1 and gs = 2 we have
= - B (L + 2S)
Each energy level is split into 2j +1 levels, corresponding to the possible values of mj . For the
usual laboratory magnetic fields, which are weak compared with the internal magnetic field
associated with the spin-orbit effect, the level splitting is small compared with the fine-
structure splitting. Unlike the case of the singlet levels in the normal effect, the Zeeman
splitting of these levels depends on j, l and s, and in general there are more than three
different transition energies due to the fact that the upper and lower states are split by
different amounts. The level splitting, that is, the energy shift relative to the position of the
no-field energy level, can be written
E = gmja eUB 2me b = gmj BB
where g, called the Land g factor is given by
g = 1 + [j(j+1)+s(s+1)-l(l+1)]/2
Note that for s = 0, j =1, and g = 1, Equation gives the splitting in the normal Zeeman effect,
as you would expect.
In 1921, two experimental physicists in Tbingen, Friedrich Paschen (18651947)
and Ernst Back (18811959), observed that
with strongly increasing magnetic field strength, the complicated multiplets of
the anomalous Zeeman effect change into the simpler patterns typical of the
normal Zeeman effect (see Fig. 1). Initially, this observation remained
With the discovery of spin in late 1925, however, and the realization that the
anomalous Zeeman effect is characteristic of systems with spin S >0, whereas the
normal Zeeman effect governs atoms with a total S = 0, the PaschenBack effect
could be understood as a decoupling of S and orbital angular momentum L, since
the influence of the total spin becomes neglectable for diminishing spin-orbit
In the strong-field case, S and L couple more strongly to the external magnetic field
than to each other, and can be visualized as independently precessing about the
external field direction.
For reference, the sodium Zeeman effect is reproduced below to show the nature of
the magnetic interaction for weak external magnetic fields.

The following is a model of the changes in the pattern if the magnetic field were strong enough to
decouple L and S. The resulting spectrum would be a triplet with the center line twice the intensity of
the outer lines.
To create this pattern, the projections of L and S in the z-direction have been
treated independently and the ms multiplied by the spin g-factor. The energy
shift is expressed as a multiple of the Bohr magneton mB. The selection rules
explain why the transitions shown are allowed and others not.Sodium was
used as the basis of the model for convenience, but the fields required to
create Paschen-Back conditions for sodium are unrealistically high. Lithium,
on the other hand, has a spin-orbit splitting of only 0.00004 eV compared to
0.0021 eV for sodium. Such small energy values are sometimes expressed in
"wavenumbers", or 1/l in cm-1. In these units the lithium separation is about
0.3 cm-1and the sodium separation is about 17 cm-1 .The Paschen-Back
conditions are met in some lithium spectra observed on the Sun, so this
effect does have astronomical significance.

Zeeman effect on a sunspot spectral line

George Ellery Hale was the first to notice the Zeeman
effect in the solar spectra, indicating the existence of
strong magnetic fields in sunspots. Such fields can be
quite high, on the order of 0.1 tesla or higher. Today, the
Zeeman effect is used to produce magnetograms showing
the variation of magnetic field on the sun.
Laser cooling
The Zeeman effect is utilized in many laser
cooling applications such as a magneto-optical trap and
the Zeeman slower.