n.
The splitting of single spectral lines of an emission spectrum into three or more polarized components when the radiation source is in a magnetic field.
[After Pieter ZEEMAN.]
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[After Pieter ZEEMAN.]
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A splitting of spectral lines when the light source being studied is placed in a magnetic field. Discovered by P. Zeeman in 1896, the effect furnishes information of prime importance in the analysis of spectra. Each kind of spectral term has its characteristic mode of splitting, and the types of terms are most definitely identified by this property, Furthermore, the effect allows an evaluation of the ratio of charge to mass of the electron and an evaluation of its precise magnetic moment.
The normal Zeeman effect is a splitting into two or three lines, depending on the direction of observation, as shown in the illustration. The light of these components is polarized in ways indicated in the illustration. The normal effect is observed for all lines belonging to singlet systems, those for which the spin quantum number S = 0. The change of frequency of the shifted components can be evaluated on classical electromagnetic principles.

Triplet observed in normal Zeeman effect. ν0 = unshifted frequency; Δνn = frequency shift.
The anomalous Zeeman effect is a more complicated type of line splitting, so named because it did not agree with the predictions of classical theory. It occurs for any spectral line arising from a combination of terms of multiplicity greater than one. Since multiplicity in spectral lines is caused by the presence of a resultant spin vector S of the electrons, the anomalous effect must be attributed to a nonclassical magnetic behavior of the electron spin.
The quadratic Zeeman effect, which depends on the square of the field strength, is of two kinds. The first results from second-order terms, and the second from the diamagnetic reaction of the electron when revolving in large orbits.
The inverse Zeeman effect is the Zeeman effect of absorption lines. It is closely related to the Faraday effect, the rotation of plane-polarized light by matter situated in a magnetic field. See also Faraday effect.
The Zeeman effect in molecules is, in general, so small as to be unobservable, even for molecules which have a permanent magnetic moment. An exception occurs for some light molecules where the magnetic moment is coupled so lightly to the frame of the molecule that it can orient itself freely in the magnetic field just as for atoms.
A clear Zeeman effect also can be observed in many crystals with sharp spectrum lines in absorption or fluorescence. Such crystals are found particularly among rare-earth salts.
The magnetic moment of the nucleus causes a Zeeman splitting in atomic spectra which is of an order of magnitude a thousand times smaller than the ordinary Zeeman effect. This Zeeman effect of the hyperfine structure usually is modified by a nuclear Paschen-Back effect. See also Paschen-Back effect.
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The Zeeman effect (IPA: [ˈzeːmɑn], in English sometimes pronounced /ˈzeɪmən/) is the splitting of 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. The Zeeman effect is very important in applications such as nuclear magnetic resonance spectroscopy, electron spin resonance spectroscopy, magnetic resonance imaging (MRI) and Mössbauer spectroscopy. It may also be utilized to improve accuracy in Atomic absorption spectroscopy.
When the spectral lines are absorption lines, the effect is called Inverse Zeeman effect.
The Zeeman effect is named after the Dutch physicist Pieter Zeeman.
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In most atoms, there exist several electron configurations with the same energy, so that transitions between these configurations and another correspond to a single spectral line. The presence of a magnetic field breaks this degeneracy, since the magnetic field interacts differently with electrons with different quantum numbers, slightly modifying their energies. The result is that, where there were several configurations with the same energy, they now have different energies, giving rise to several very close spectral lines.
Without a magnetic field, configurations a, b and c have the same energy, as do d, e and f. The presence of a magnetic field (B) splits the energy levels. Therefore, a line produced by a transition from a, b or c to d, e or f will now be split into several components between different combinations of a, b, c and d, e, f. However, not all transitions will be possible (in the dipole approximation), as governed by the selection rules.
Since the distance between the Zeeman sub-levels is proportional to the magnetic field, this effect can be used by astronomers to measure the magnetic field of the Sun and other stars.
There is also an anomalous Zeeman effect 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's an uneven number of electrons involved. 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.
If the magnetic field strength is too high, the effect is no longer linear; at even higher field strength, electron coupling is disturbed and the spectral lines rearrange. This is called the Paschen-Back effect.
The total Hamiltonian of an atom in a magnetic field is

where H0 is the unperturbed Hamiltonian of the atom, and VM is perturbation due to the magnetic field:

where
is the magnetic moment of the atom. The magnetic moment consists of the electronic and nuclear parts, however, the latter is many orders of magnitude smaller and will be neglected further on. Therefore,

where μB is the Bohr magneton,
is the total electronic angular momentum, and g is the g-factor. The operator of the magnetic moment of an electron is a sum of the contributions of the orbital angular momentum
and the spin angular momentum
, with each multiplied by the appropriate gyromagnetic ratio:

where gl = 1 or
(the latter is called the anomalous gyromagnetic ratio; the deviation of the value from 2 is due to Quantum Electrodynamics effects). In the case of the LS coupling, one can sum over all electrons in the atom:

where
and
are the total orbital momentum and spin of the atom, and averaging is done over a state with a given value of the total angular momentum.
If the interaction term VM is small (less than the fine structure), it can be treated as a perturbation; this is the Zeeman effect proper. In the Paschen-Back effect, described below, VM exceeds the LS coupling significantly (but is still small compared to H0). In ultrastrong magnetic fields, the magnetic-field interaction may exceed H0, in which case the atom can no longer exist in its normal meaning, and one talks about Landau levels instead. There are, of course, intermediate cases which are more complex than these limit cases.
If the spin-orbit interaction dominates over the effect of the external magnetic field,
and
are not separately conserved, only the total angular momentum
is. The spin and orbital angular momentum vectors can be thought of as precessing about the (fixed) total angular momentum vector
. The (time-)"averaged" spin vector is then the projection of the spin onto the direction of
:

and for the (time-)"averaged" orbital vector:

Thus,

Using
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)],](http://wpcontent.answers.com/math/1/b/c/1bc29c6d4f59fb4d5fa2946297f57623.png)
and: using
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)].](http://wpcontent.answers.com/math/0/e/4/0e46480c3743ad7df09614bf02499cbd.png)
Combining everything and taking
, we obtain the magnetic potential energy of the atom in the applied external magnetic field,
![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],](http://wpcontent.answers.com/math/b/c/9/bc954e9909b1793da05b1f1d56562cd3.png)
where the quantity in square brackets is the Lande g-factor gJ of the atom (gL = 1 and
) and mj is the z-component of the total angular momentum. For a single electron above filled shells s = 1 / 2.
The Lyman alpha transition in hydrogen in the presence of the spin-orbit interaction involves the transitions
and 
In the presence of an external magnetic field, the weak-field Zeeman effect splits the 1S1/2 and 2P1/2 states into 2 levels each (mj = 1 / 2, − 1 / 2) and the 2P3/2 state into 4 levels (mj = 3 / 2,1 / 2, − 1 / 2, − 3 / 2). The Lande g-factors for the three levels are:
Note in particular that the size of the energy splitting is different for the different orbitals, because the gJ values are different. On the left, fine structure splitting is depicted. This splitting occurs even in the absence of a magnetic field, as it is due to spin-orbit coupling. Depicted on the right is the additional Zeeman splitting, which occurs in the presence of magnetic fields.
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 sufficiently large to disrupt the coupling between orbital(l) and spin angular momenta(s). This effect is the strong field generalization of the Zeeman effect. The effect was named after the German physicists Friedrich Paschen and Ernst E. A. Back.
When the magnetic-field perturbation significantly exceeds the spin-orbit interaction, one can safely assume [H0,S] = 0. This allows the expectation values of Lz and Sz to be easily evaluated for a state
:

The above may be read as implying that the LS-coupling is completely broken by the external field. The ml and ms are still "good" quantum numbers. Together with the selection rules for an electric dipole transition, i.e.,
this allows to ignore the spin degree of freedom altogether. As a result, only three spectral lines will be visible, corresponding to the
selection rule. The splitting ΔE = BμBΔml is independent of the unperturbed energies and electronic configurations of the levels being considered.
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