Zeeman effect

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The Zeeman effect (/'ze?m?n/; IPA: ['ze?m?n]), named after the Dutch physicist P
ieter Zeeman, is the effect of splitting a spectral line into several components
in the presence of a static magnetic field. It is analogous to the Stark effect
, the splitting of a spectral line into several components in the presence of an
electric field. Also similar to the Stark effect, transitions between different
components have, in general, different intensities, with some being entirely fo
rbidden (in the dipole approximation), as governed by the selection rules.
Since the distance between the Zeeman sub-levels is a function of the magnetic f
ield, this effect can be used to measure the magnetic field, e.g. that of the Su
n and other stars or in laboratory plasmas. The Zeeman effect is very important
in applications such as nuclear magnetic resonance spectroscopy, electron spin r
esonance spectroscopy, magnetic resonance imaging (MRI) and Mssbauer spectroscopy
. It may also be utilized to improve accuracy in atomic absorption spectroscopy.
A theory about the magnetic sense of birds assumes that a protein in the retina
is changed due to the Zeeman effect.[1]
When the spectral lines are absorption lines, the effect is called inverse Zeema
n effect.
Zeeman splitting of the 5s level of Rb-87, including fine structure and hyperfin
e structure splitting. Here F = J + I, where I is the nuclear spin. (for Rb-87,
I = 3/2)
Contents [hide]
1 Nomenclature
2 Theoretical presentation
3 Weak field (Zeeman effect)
3.1 Example: Lyman alpha transition in hydrogen
4 Strong field (Paschen-Back effect)
5 Intermediate field for j = 1/2
6 Applications
6.1 Astrophysics
6.2 Laser Cooling
7 See also
8 References
8.1 Historical
8.2 Modern
9 External links
Nomenclature[edit]
Historically, one distinguishes between the normal and an anomalous Zeeman effec
t that appears on transitions where the net spin of the electrons is not 0, the
number of Zeeman sub-levels being even instead of odd if there is an uneven numb
er of electrons involved. It was called "anomalous" because the electron spin ha
d not yet been discovered, and so there was no good explanation for it at the ti
me that Zeeman observed the effect.
At higher magnetic fields the effect ceases to be linear. At even higher field s
trength, when the strength of the external field is comparable to the strength o
f the atom's internal field, electron coupling is disturbed and the spectral lin
es rearrange. This is called the Paschen-Back effect.
In the modern scientific literature, these terms are rarely used, with a tendenc
y to use just the "Zeeman effect".
Theoretical presentation[edit]

The total Hamiltonian of an atom in a magnetic field is

H = H_0 + V_M,\
where H_0 is the unperturbed Hamiltonian of the atom, and V_M is perturbation du
e to the magnetic field:
V_M = -\vec{\mu} \cdot
where \vec{\mu} is the
of the electronic and
itude smaller and will

\vec{B},
magnetic moment of the atom. The magnetic moment consists
nuclear parts; however, the latter is many orders of magn
be neglected here. Therefore,

\vec{\mu} \approx -\frac{\mu_B g \vec{J}}{\hbar},

where \mu_B is the Bohr magneton, \vec{J} is the total electronic angular moment
um, and g is the Land g-factor. A more accurate approach is to take into account
that the operator of the magnetic moment of an electron is a sum of the contribu
tions of the orbital angular momentum \vec L and the spin angular momentum \vec
S, with each multiplied by the appropriate gyromagnetic ratio:
\vec{\mu} = -\frac{\mu_B (g_l \vec{L} + g_s \vec{S})}{\hbar},
where g_l = 1 and g_s \approx 2.0023192 (the latter is called the anomalous gyro
magnetic ratio; the deviation of the value from 2 is due to Quantum Electrodynam
ics effects). In the case of the LS coupling, one can sum over all electrons in
the atom:
g \vec{J} = \left\langle\sum_i (g_l \vec{l_i} + g_s \vec{s_i})\right\rangle = \l
eft\langle (g_l\vec{L} + g_s \vec{S})\right\rangle,
where \vec{L} and \vec{S} are the total orbital momentum and spin of the atom, a
nd averaging is done over a state with a given value of the total angular moment
um.
If the interaction term V_M is small (less than the fine structure), it can be t
reated as a perturbation; this is the Zeeman effect proper. In the Paschen-Back
effect, described below, V_M exceeds the LS coupling significantly (but is still
small compared to H_{0}). In ultrastrong magnetic fields, the magnetic-field in
teraction may exceed H_0, in which case the atom can no longer exist in its norm
al meaning, and one talks about Landau levels instead. There are, of course, int
ermediate cases which are more complex than these limit cases.
Weak field (Zeeman effect)[edit]
If the spin-orbit interaction dominates over the effect of the external magnetic
field, \scriptstyle \vec L and \scriptstyle \vec S are not separately conserved
, only the total angular momentum \scriptstyle \vec J = \vec L + \vec S is. The
spin and orbital angular momentum vectors can be thought of as precessing about
the (fixed) total angular momentum vector \scriptstyle \vec J. The (time-)"avera
ged" spin vector is then the projection of the spin onto the direction of \scrip
tstyle \vec J:
\vec S_{avg} = \frac{(\vec S \cdot \vec J)}{J^2} \vec J
and for the (time-)"averaged" orbital vector:
\vec L_{avg} = \frac{(\vec L \cdot \vec J)}{J^2} \vec J.
Thus,
\langle V_M \rangle = \frac{\mu_B}{\hbar} \vec J(g_L\frac{\vec L \cdot \vec J}{J
^2} + g_S\frac{\vec S \cdot \vec J}{J^2}) \cdot \vec B.
Using \scriptstyle \vec L = \vec J - \vec S and squaring both sides, we get
\vec S \cdot \vec J = \frac{1}{2}(J^2 + S^2 - L^2) = \frac{\hbar^2}{2}[j(j+1) l(l+1) + s(s+1)],
and: using \scriptstyle \vec S = \vec J - \vec L and squaring both sides, we get

\vec L \cdot \vec J = \frac{1}{2}(J^2 - S^2 + L^2) = \frac{\hbar^2}{2}[j(j+1) +

l(l+1) - s(s+1)].
Combining everything and taking \scriptstyle J_z = \hbar m_j, we obtain the magn
etic potential energy of the atom in the applied external magnetic field,
\begin{align}
V_M
&= \mu_B B m_j \left[ g_L\frac{j(j+1) + l(l+1) - s(s+1)}{2j(j+1)} + g_S\frac{j(j
+1) - l(l+1) + s(s+1)}{2j(j+1)} \right]\\
&= \mu_B B m_j \left[1 + (g_S-1)\frac{j(j+1) - l(l+1) + s(s+1)}{2j(j+1)} \right]
,
\\
&= \mu_B B m_j g_j
\end{align}
where the quantity in square brackets is the Land g-factor gJ of the atom (g_L =
1 and g_S \approx 2) and m_j is the z-component of the total angular momentum. F
or a single electron above filled shells s = 1/2 and j = l \pm s , the Land g-fa
ctor can be simplified into:
g_j = 1 \pm \frac{g_S-1}{2l+1}
Example: Lyman alpha transition in hydrogen[edit]
The Lyman alpha transition in hydrogen in the presence of the spin-orbit interac
tion involves the transitions
2P_{1/2} \to 1S_{1/2} and 2P_{3/2} \to 1S_{1/2}.
In the presence of an external magnetic field, the weak-field Zeeman effect spli
ts the 1S1/2 and 2P1/2 levels into 2 states each (m_j = 1/2, -1/2) and the 2P3/2
level into 4 states (m_j = 3/2, 1/2, -1/2, -3/2). The Land g-factors for the thr
ee levels are:
g_J = 2 for 1S_{1/2} (j=1/2, l=0)
g_J = 2/3 for 2P_{1/2} (j=1/2, l=1)
g_J = 4/3 for 2P_{3/2} (j=3/2, l=1).
Note in particular that the size of the energy splitting is different for the di
fferent orbitals, because the gJ values are different. On the left, fine structu
re splitting is depicted. This splitting occurs even in the absence of a magneti
c field, as it is due to spin-orbit coupling. Depicted on the right is the addit
ional Zeeman splitting, which occurs in the presence of magnetic fields.
Zeeman p s doublet.svg
Strong field (Paschen-Back effect)[edit]
The Paschen-Back effect is the splitting of atomic energy levels in the presence
of a strong magnetic field. This occurs when an external magnetic field is suff
iciently large to disrupt the coupling between orbital (\vec L) and spin (\vec S
) angular momenta. This effect is the strong-field limit of the Zeeman effect. W
hen s = 0, the two effects are equivalent. The effect was named after the German
physicists Friedrich Paschen and Ernst E. A. Back.[2]
When the magnetic-field perturbation significantly exceeds the spin-orbit intera
ction, one can safely assume [H_{0}, S] = 0. This allows the expectation values
of L_{z} and S_{z} to be easily evaluated for a state |\psi\rangle . The energie
s are simply:
E_{z} = \langle \psi| \left( H_{0} + \frac{B_{z}\mu_B}{\hbar}(L_{z}+g_{s}S_z) \
right) |\psi\rangle = E_{0} + B_z\mu_B (m_l + g_{s}m_s).
The above may be read as implying that the LS-coupling is completely broken by t
he external field. However m_l and m_s are still "good" quantum numbers. Togethe

r with the selection rules for an electric dipole transition, i.e., \Delta s = 0
, \Delta m_s = 0, \Delta l = \pm 1, \Delta m_l = 0, \pm 1 this allows to ignore
the spin degree of freedom altogether. As a result, only three spectral lines wi
ll be visible, corresponding to the \Delta m_l = 0, \pm 1 selection rule. The sp
litting \Delta E = B \mu_B \Delta m_l is independent of the unperturbed energies
and electronic configurations of the levels being considered. It should be note
d that in general (if s \ne 0), these three components are actually groups of se
veral transitions each, due to the residual spin-orbit coupling.
In general, one must now add spin-orbit coupling and relativistic corrections (w
hich are of the same order, known as 'fine structure') as a perturbation to thes
e 'unperturbed' levels. First order perturbation theory with these fine-structur
e corrections yields the following formula for the Hydrogen atom in the PaschenBack limit:[3]
E_{z+fs} = E_{z} + \frac{\alpha^2}{2 n^3} \left[ \frac{3}{4n} - \left( \frac{l(
l+1) - m_l m_s}{l(l+1/2)(l+1) } \right)\right]
Intermediate field for j = 1/2[edit]
In the magnetic dipole approximation, the Hamiltonian which includes both the hy
perfine and Zeeman interactions is
H = h A \vec I \cdot \vec J - \vec \mu \cdot \vec B
H = h A \vec I \cdot\vec J + \mu_B (g_J\vec J + g_I\vec I ) \cdot \vec
B
To arrive at the Breit-Rabi formula we will include the hyperfine structure (int
eraction between the electron's spin and the magnetic moment of the nucleus), wh
ich is governed by the quantum number F \equiv |\vec F| = |\vec J + \vec I|, wh
ere \vec I is the spin angular momentum operator of the nucleus. Alternatively,
the derivation could be done with J only. The constant A is known as the zero fi
eld hyperfine constant and is given in units of Hertz. \mu_B is the Bohr magneto
n. \hbar\vec J and \hbar\vec I are the electron and nuclear angular momentum ope
rators. g_J and g_F can be found via a classical vector coupling model or a more
detailed quantum mechanical calculation to be:
g_J = g_L\frac{J(J+1) + L(L+1) - S(S+1)}{2J(J+1)} + g_S\frac{J(J+1) - L(L+1) +
S(S+1)}{2J(J+1)}
g_F = g_J\frac{F(F+1) + J(J+1) - I(I+1)}{2F(F+1)} + g_I\frac{F(F+1) - J(J+1) +
I(I+1)}{2F(F+1)}
As discussed, in the case of weak magnetic fields, the Zeeman interaction can be
treated as a perturbation to the |F,m_f \rangle basis. In the high field regime
, the magnetic field becomes so large that the Zeeman effect will dominate, and
we must use a more complete basis of |I,J,m_I,m_J\rangle or just |m_I,m_J \rangl
e since I and J will be constant within a given level.
To get the complete picture, including intermediate field strengths, we must con
sider eigenstates which are superpositions of the |F,m_F \rangle and |m_I,m_J \
rangle basis states. For J = 1/2, the Hamiltonian can be solved analytically, r
esulting in the Breit-Rabi formula. Notably, the electric quadrapole interaction
is zero for L = 0 (J = 1/2), so this formula is fairly accurate.
To solve this system, we note that at all times, the total angular momentum proj
ection m_F = m_J + m_I will be conserved. Furthermore, since J = 1/2 between sta
tes m_J will change between only \pm 1/2. Therefore, we can define a good basis
as:
|\pm\rangle \equiv |m_J = \pm 1/2, m_I = m_F \mp 1/2 \rangle
We now utilize quantum mechanical ladder operators, which are defined for a gene
ral angular momentum operator L as
L_{\pm} \equiv L_x \pm iL_y

These ladder operators have the property

L_{\pm}|L_,m_L \rangle = \sqrt{(L \mp m_L)(L \pm m_L +1)} |L,m_L \pm 1 \rangle
as long as m_L lies in the range {-L, \dots ... ,L} (otherwise, they return zero
). Using ladder operators J_{\pm} and I_{\pm} We can rewrite the Hamiltonian as
H = h A I_z J_z + \frac{hA}{2}(J_+ I_- + J_- I_+) + \mu_B B(g_J J_z + g_I I_Z)
Now we can determine the matrix elements of the Hamiltonian:
\langle \pm |H|\pm \rangle = -\frac{1}{4}A + \mu_B B g_I m_F \pm \frac{1}{2} (h
Am_F + \mu_B B (g_J-g_I))
\langle \pm |H| \mp \rangle = \frac{1}{2} hA \sqrt{(I + 1/2)^2 - m_F^2}
Solving for the eigenvalues of this matrix, (as can be done by hand, or more eas
ily, with a computer algebra system) we arrive at the energy shifts:
\Delta E_{F=I\pm1/2} = -\frac{h \Delta W }{2(2I+1)} + \mu_B g_I m_F B \pm \fra
c{h \Delta W}{2}\sqrt{1 + \frac{2m_F x }{I+1/2}+ x^2 }
x \equiv \frac{\mu_B B(g_J - g_I)}{h \Delta W} \quad \quad \Delta W= A \left(I+\
frac{1}{2}\right)
where \Delta W is the splitting (in units of Hz) between two hyperfine sublevels
in the absence of magnetic field B,
x is referred to as the 'field strength parameter' (Note: for m = -(I+1/2) the s
quare root is an exact square, and should be interpreted as +(1-x)). This equati
on is known as the Breit-Rabi formula and is useful for systems with one valence
electron in an s (J = 1/2) level.[4][5]
Note that index F in \Delta E_{F=I\pm1/2} should be considered not as total angu
lar momentum of the atom but as asymptotic total angular momentum. It is equal t
o total angular momentum only if B=0 otherwise eigenvectors corresponding differ
ent eigenvalues of the Hamiltonian are the superpositions of states with differe
nt F but equal m_F (the only exceptions are |F=I+1/2,m_F=\pm F \rangle).
Applications[edit]
Astrophysics[edit]
Zeeman effect on a sunspot spectral line
George Ellery Hale was the first to notice the Zeeman effect in the solar spectr
a, indicating the existence of strong magnetic fields in sunspots. Such fields c
an 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 s
un.
Laser Cooling[edit]
The Zeeman effect is utilized in many Laser cooling applications such as a Magne
to-optical trap and the Zeeman slower.
See also[edit]
Magneto-optic Kerr effect
Voigt effect
Faraday effect
Cotton-Mouton effect
Polarization spectroscopy
Zeeman energy
Lamb shift
Electron configuration says at subshell p (l=1), there are 3 energy level ml=-1,
0,1, but we see only two p1/2 and p3/2. for subshell s(l=0), there is only 1 ene
rgy level (ml=0), but here we have 2. l corresponding to fine structure, ml corr
esponding to hyperfine structure.
References[edit]

Jump up ^ The magnetic compass mechanisms of birds and rodents are based on diff
erent physical principles. Journal of the Royal Society
Jump up ^ Paschen, F., Back, E.: Liniengruppen magnetisch vervollstndigt. Physica
1, 261 273 (1921).
Jump up ^ Griffiths, David J. (2004). Introduction to Quantum Mechanics (2nd ed.
). Prentice Hall. p. 247. ISBN 0-13-111892-7. OCLC 40251748.
Jump up ^ Woodgate, Elementary Atomic Structure, section 9.
Jump up ^ first appeared in G. Breit and I. Rabi, Phys. rev. 38, 2082 (1931).
Historical[edit]
Condon, E. U.; G. H. Shortley (1935). The Theory of Atomic Spectra. Cambridge Un
iversity Press. ISBN 0-521-09209-4. (Chapter 16 provides a comprehensive treatme
nt, as of 1935.)
Zeeman, P. (1897). "On the influence of Magnetism on the Nature of the Light emi
tted by a Substance". Phil. Mag. 43: 226.
Zeeman, P. (1897). "Doubles and triplets in the spectrum produced by external ma
gnetic forces". Phil. Mag. 44 (266): 55. doi:10.1080/14786449708621028.
Zeeman, P. (11 February 1897). "The Effect of Magnetisation on the Nature of Lig
ht Emitted by a Substance". Nature 55 (1424): 347. Bibcode:1897Natur..55..347Z.
doi:10.1038/055347a0.
Modern[edit]
Feynman, Richard P., Leighton, Robert B., Sands, Matthew (1965). The Feynman Lec
tures on Physics, Vol. 3. Addison-Wesley. ISBN 0-201-02115-3.
Forman, Paul (1970). "Alfred Land and the anomalous Zeeman Effect, 1919-1921". Hi
storical Studies in the Physical Sciences 2: 153 261. doi:10.2307/27757307.
Griffiths, David J. (2004). Introduction to Quantum Mechanics (2nd ed.). Prentic
e Hall. ISBN 0-13-805326-X.
Liboff, Richard L. (2002). Introductory Quantum Mechanics. Addison-Wesley. ISBN
0-8053-8714-5.
Sobelman, Igor I. (2006). Theory of Atomic Spectra. Alpha Science. ISBN 1-84265203-6.
Foot, C. J. (2005). Atomic Physics. ISBN 0-19-850696-1.
External links[edit]
Wikimedia Commons has media related to Zeeman effect.
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