The Zeeman Effect January 21, 2019

The Zeeman Effect

Notes and cautions

• Do not look directly at the mercury light source. It is contained in a quartz tube. The ultraviolet
radiation is not absorbed in the quartz and could damage your eyes.
• Notice the exposed terminals on the magnet. The power supply voltage is high enough, and the
current capacity is such, that you should be cautious.
• Do not keep the current through the magnet at high values for long periods of time. The magnet
could overheat. As soon as you have taken your high-field data, turn the current back to zero.
• The Gaussmeter probe can be damaged easily. Handle it with care.

1 Introduction
Michael Faraday was the first to attempt to observe an effect of magnetic fields on atomic spectra. In 1862
he looked at sodium flames, but could see no change when a strong magnetic field was applied. The effect
was too small for his spectrometer to resolve. Several others tried with improved spectrometers, but it was
not until 1896 that Pieter Zeeman finally succeeded. His experiments with sodium in magnetic fields of
the order of 1 T showed that the spectral lines at 589.6 and 589.0 nm (the sodium D lines) split into four
and six components respectively when the magnetic field was applied. Zeeman developed a classical theory
based on an oscillating charge in a magnetic field. According to classical theory, an oscillating charge emits
radiation at the frequency of oscillation, resulting in a single spectral line. Zeeman added a magnetic force
to the three-dimensional harmonic oscillator equation and showed that the application of a magnetic field
should result in the single spectral line being split into three components. Some spectral lines did indeed split
into three components in a magnetic field, and this phenomenon came to be known as the normal Zeeman
effect. Most lines, however, split into more than three components and such lines were said to exhibit
the anomalous Zeeman effect. The full explanation of the Zeeman effect had to await the development of
quantum mechanics and the discovery of electron spin. The explanation of the Zeeman effect was one of the
early triumphs of quantum mechanics. Today the terms normal and anomalous do not accurately describe
our understanding of the Zeeman effect since the “anomalous” effect is understood as well as the “normal”
effect, but the historical terms remain in common usage.

2 Origin of the Zeeman Effect

The Zeeman effect occurs due to the interaction of the net magnetic moment µ of an atom with an external
magnetic field B. The operator H1 representing the interaction is given by

H1 = −µ · B. (1)

For ordinary magnetic fields this interaction is relatively small and may be treated as a perturbation. It is
necessary to express µ in terms of angular momentum operators. According to quantum mechanics, each
electron i has a spin angular momentum operator si and an orbital angular momentum operator `i . In the LS
coupling scheme (see books on quantum mechanics for more details) the net magnetic moment of a multi-
electron atom may be found by (i) adding vectorially the magnetic moments due to the orbital motion of
each electron to find the total moment due to orbital angular momentum, (ii) adding vectorially the magnetic

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moments due to the spin of each electron to find the total moment due to spin and (iii) adding the total spin
moment and total orbital moment to get the total magnetic moment of the atom,
1e e 1e
µ = − ∑ `i − ∑ si = − (L + 2S)
2m i m i 2m
1e
µ = − (J + S) (2)
2m
Here, e represents the magnitude of the charge on the electron, m is the mass of the electron, the sum is
over all the electrons of the atom, L is the total orbital angular momentum operator, S is the total spin
angular momentum operator, and J = L + S represents the total angular momentum operator for the atom.
Substituting Eq. 2 into Eq. 1 gives
e
H1 = (J + S) · B. (3)
2m
The rigorous quantum mechanical treatment of this problem is too lengthy to present here; however,
a simple physical approximation leads to the correct result. Due to spin-orbit coupling S and L are not
constant; rather, each precesses about J . In the absence of a magnetic field, J is constant. When a magnetic
field is applied J will precess about B. For fields which are not too strong the precession of L and S about
J will be much faster than the precession of J about B. Thus, in Eq. 3 for S we use Savg , the projection of
S along J ,
S ·J
Savg = J. (4)
J2
We evaluate the term S · J as follows. Using L2 = L · L = (J − S) · (J − S) = J 2 + S 2 − 2S · J gives
S · J = (J 2 + S 2 − L2 )/2. Then,

J 2 + S 2 − L2
J + S ≈ J + Savg = J + J. (5)
2J 2
Substituting Eq. 5 into Eq. 3 and using J · B = Jz B gives

J 2 + S 2 − L2
 
eB
H1 = 1+ Jz (6)
2m 2J 2

To calculate the first-order shift of the atomic energy levels due to the Zeeman effect it is only necessary
to calculate the expectation value of H1 . This calculation is easy because the expectation values of the
operators in Eq. 6 are known. They are hJ2 i = j( j + 1)h̄2 , hS2 i = s(s + 1)h̄2 , hL2 i = `(` + 1)h̄2 , and hJz i =
m j h̄. and Here `, s, and j are integers or half-integers characterizing the orbital, spin, and total angular
momentum respectively, and m j = j, j − 1, . . . − j. The shift of the energy levels giving rise to the Zeeman
effect becomes  
eh̄
Ej = gj Bm j (7)
2m
where
j( j + 1) + s(s + 1) − `(` + 1)
gj = 1+ (8)
2 j( j + 1)
is called the Landé g-factor. The quantity eh̄/2m is called the Bohr magneton µB and has the value 9.274 ×
10−24 J/T. Equations 7 and 8 are the basic relations used to interpret the Zeeman effect.
Each different combination of (n, j, `, s, m j ) represents a different state for the electrons in an atom (n is
the principal quantum number). For full shells j, `, and s all equal zero. Generally, the different states have
different energies. In the absence of a magnetic field, states with the same (n, j, `, s) but different m j have

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The Zeeman Effect January 21, 2019

the same energy. Because there are 2 j + 1 possible m j values for each j, Eq. 7 shows that the application of
a magnetic field will split a single energy level into 2 j + 1 different levels.
Each state is specified by a spectroscopic symbol, such as 4f 5d3 H5 . The first term gives the one-electron
states (4f 5d) of the valence electrons; the second term gives s, ` and j according to spectroscopic notation.
The superscript is equal to 2s + 1, the capital letters S, P, D, F, G, H etc. refer to ` = 0, 1, 2, 3, 4, 5 etc.,
and the subscript is equal to j. Thus, in the example given there are two electrons outside a closed shell and
these combine to give s = 1, ` = 5, and j = 5.

Figure 1: Energy level diagram illustrating the normal Zeeman effect. The vertical dashed and solid lines represent
transitions with ∆m j = 0 and ∆m j = ±1 respectively.

We now have the background needed to understand the Zeeman effect. Two examples will be given
before considering the experiment to be performed. Figure 1 illustrates part of the energy level diagram of
an atom which exhibits the “normal” Zeeman effect. The left-hand part of the figure shows the situation in
the absence of a magnetic field. The 1 D2 state of the atom lies higher in energy than the 1 P1 state. If the atom
is excited a transition from the higher to lower state may occur with the photon energy hν = hc/λ = ∆E.
Only one wavelength is observed. If a magnetic field is applied the energy levels split. For this example,
both states haveg j = 1. (You should verify that this is the case before proceeding further.) The 1 D2 level
splits into five levels with a level separation of µB B, while the 1 P1 state splits into three levels with the same
level separation. (You should also verify these statements before proceeding further.)
If the atom is excited there may be transitions from the upper levels to the lower levels. However, a
selection rule applies. Only those transitions in which m j changes by 0 or ±1 are allowed. The dotted lines
in Fig. 1 correspond to transitions with ∆m j = 0. The photon energy for these transitions is the same as in
zero magnetic field. The three transitions illustrated on the left correspond to ∆m j = +1. The photon energy
for all three transitions is the same, and is µB B less than the zero field case. Finally, the three transitions on
the right correspond to ∆m j = −1 and all three have a photon energy which is µB B higher than the zero field
case. Of course, you should work all of this out yourself. You can see that the zero field line splits into three
components with the application of a magnetic field, and this is usually called the normal Zeeman effect.
Figure 2 illustrates part of an energy level diagram for an atom which exhibits the “anomalous” Zeeman
effect. In this case a 3 D2 state and a 3 P1 state are shown. You should verify that the g j values are as given on
the right. The energy level separation of the upper states is 7µB B/6 while that of the lower states is 3µB B/2.
The photon energy shifts, relative to the zero field transition, are indicated at the bottom of the diagram and

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The Zeeman Effect January 21, 2019

range from −9µB B/6 to 9µB B/6. Of course you should verify that this is true. Notice that the original
single line in zero field is now split into nine lines! This situation illustrates the anomalous Zeeman effect.
What is the crucial difference between Figs. 1 and 2 which gives nine lines in one case, but only three in the
other?

Figure 2: Energy level diagram illustrating the anomalous Zeeman effect.

3 Mercury Spectrum
In this experiment we will study the Zeeman effect in mercury. The electron configuration of mercury is the
ground state is

1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p6 4f14 5d10 6s2 .

These are all filled subshells, thus the ground state of mercury has zero spin and zero orbital angular mo-
mentum. The excited levels involved in the optical spectrum consist of one of the 6s electrons being raised
to a higher energy state, for example 6p. The two electrons (the remaining 6s electron and the electron in
the higher energy state) can then give a total spin of the atom of either 0 or 1. Various combinations of spin,
orbital angular momentum, and total angular momentum are possible. These combinations are designated
by terms such as 1 S0 , 3 P2 , 3 P1 .
The lowest energy states in mercury are shown in Fig. 3. The strongest visible and ultraviolet spectral
lines are also indicated. The wavelengths of the transitions are indicated in nm. The most convenient line to
work with in this experiment is the 579.066 nm transition from 6s6d1 D2 to 6s6p1 P1 . With the spectrometer
used in this experiment it will not be possible to resolve the 579.066 and the nearby 578.969 nm lines.
Fortunately, the 578.969 nm line is quite weak. Most of the light you see at 579 nm is due to the 579.066
nm line. Therefore, you can ignore the 578.969 nm line in your analysis.
Before coming to lab you should figure out how many spectral components there will be in the 579.066
nm line when a magnetic field is turned on, and how large the splitting will be in a magnetic field of about
1 T.

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The Zeeman Effect January 21, 2019

Violet Green

w1

w2
lo
Yel

lo
Yel
Figure 3: Energy level diagram of mercury (not to scale, splittings are expanded for clarity). Wavelengths of several spectral
lines are given in nm.

4 Experimental Apparatus and Procedure

The experimental arrangement is shown in Fig. 4. A lens is used to focus light from the mercury lamp onto
an adjustable spectrometer slit. A collimator lens focuses an image of the slit further down the optical train.
The light then passes through the Fabry-Pérot interferometer and then into the spectrometer, where the light
is split into its spectral lines by a prism. The image of the slit is inside the focussing tube, where it can be
examined by either the eyepiece or the video camera.

Figure 4: Experimental apparatus for the Zeeman effect experiment.

Begin by inserting the eyepiece and looking for the various spectral lines. The large dial on the spec-
trometer can be turned to center the desired line in the eyepiece. Then the eyepiece can be swapped out for
the camera. It will help if you open the slit until the yellow lines are almost overlapping. The wavelength
shifts due to the Zeeman effect are quite small, and cannot be resolved by the spectrometer alone. Thus a
high-resolution Fabry-Pérot interferometer is used. It consists of two precisely parallel reflecting surfaces, as
shown in Fig. 5. You will probably want to consult additional reference material, such as an optics textbook,
in order to understand the Fabry-Pérot interferometer better.

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The Zeeman Effect January 21, 2019

Figure 5: Fabry-Pérot interferometer. The various reflected beams emerging from the right side interfere to produce the
patterns illustrated in Fig. 6.

If the light entering the Fabry-Pérot interferometer in Fig. 5 is of a single wavelength λ , rings of inter-
ference maxima will be seen in the emerging light at angles θ given by 2L cos θ = mλ where m is an integer.
L is the optical path length of the interferometer (the actual length times the index of refraction). How sharp
the rings appear depends on the reflectivity R of the reflecting surfaces and the quality of the collimator.
When the magnetic field is turned off (one wavelength case) you should see through the eyepiece a vertical
slice of the circular pattern shown in Fig. 6a.

a b c
Figure 6: Fabry-Pérot interference patterns. The solid and dashed lines represent two different wavelengths. (a) One
wavelength; (b) two wavelengths with ∆ν = (c/2L)(∆m + 1/2); (c) two wavelengths with ∆ν = (c/2L)∆m, where ∆m is an
integer.

With two or more wavelengths entering the Fabry-Pérot interferometer, you should see a superposition
of the two or more ring patterns, as in Fig. 6b. When the two ring patterns happen to coincide, as in Fig. 6c,
you should get rings that are as sharp as when you only had one wavelength. This coincidence provides a
convenient means to measure the separation of two closely spaced spectral lines. The ring patterns for two
wavelengths λ and λ 0 coincide when
2L cos θ = mλ and 2L cos θ = m0 λ 0 (9)
where m and m0 are both integers. Let m0 = m + ∆m and λ 0 = λ + ∆λ . Using Eq. 9 we have mλ = (m +
∆m)(λ + ∆λ ). Solving for ∆λ and neglecting the small ∆m∆λ term we have
∆λ ∆m
− = . (10)
λ2 mλ
Differentiating the fundamental relation ν = c/λ gives
c∆λ
∆ν = − . (11)
λ2

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The Zeeman Effect January 21, 2019

Substituting mλ from Eq. 9 into Eq. 10, then combining Eqs. 10 and 11 gives
c
∆ν = ∆m, (12)
2L
where we have used the small angle approximation and set cos θ = 1. Equation 12 is the basic relation
to be used with the Fabry-Pérot interferometer. Remember that Eq. 12 applies when the interference rings
for the two spectral lines passing through the spectrometer coincide, yielding a sharp pattern as in Fig. 6c.
Remember also that ∆m is an integer. For the present case 2L = 1.0000 cm.
The resolution of the Fabry-Pérot interferometer used in the present experiment may not be sufficient
to easily resolve the lines as they split in a magnetic field. At zero field the pattern should look something
like Fig. 6a. As the field is increased the lines may become blurry. When you reach the condition shown in
Fig. 6b the lines may become sharper with twice the original number of fringes. As the field is increased
further such that Eq. 12 is satisfied the rings should become sharp again with the original number of com-
ponents. The best quantitative results can probably be obtained by looking for field values where the rings
appear sharpest.

5 Analysis and Things to Consider

1. Observe the effect of the magnetic field on the 579.066 nm line (the yellow line farthest left) in
mercury. Make quantitative measurements of the magnetic fields where the Fabry-Pérot interference
fringes become sharp. What is the value of ∆m in each case?
2. Use your results to calculate a value of e/m for the electron, as Zeeman did.
3. Observe the 579.066 nm line with a polarizer. Try it with the polarizer parallel, and perpendicular to
the magnetic field. What do you observe.
4. Consider other spectral lines, in particular the green 546.1 nm line. What do you expect for this
line? What is observed? Which lines show the normal Zeeman effect and which show the anomalous
Zeeman effect?

6 References
1. R. T. Weidner and R. L. Sells, Elementary Modern Physics, 3rd ed., Allyn and Bacon, pp. 212 -224.
2. F. K. Richtmeyer and E. H. Kennard, Introduction to Modern Physics, McGraw-Hill, 1947, pp. 75
and 365.
3. F. A. Jenkins and H. E. White, Fundamentals of Optics, 4th ed., McGraw-Hill, 1976, p. 679.

TEC/WFP 8/85
RGL 1/97
Revised 1/16 by Stuart Field