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Zeeman effect
Zeeman effect
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The spectral lines of mercury vapor lamp at wavelength 546.1 nm, showing anomalous Zeeman effect. (A) Without magnetic field. (B) With magnetic field, spectral lines split as transverse Zeeman effect. (C) With magnetic field, split as longitudinal Zeeman effect. The spectral lines were obtained using a Fabry–Pérot interferometer.
Zeeman splitting of the 5s level of 87Rb, including fine structure and hyperfine structure splitting. Here F = J + I, where I is the nuclear spin (for 87Rb, I = 32).
This animation shows what happens as a sunspot (or starspot) forms and the magnetic field increases in strength. The light emerging from the spot starts to demonstrate the Zeeman effect. The dark spectra lines in the spectrum of the emitted light split into three components and the strength of the circular polarisation in parts of the spectrum increases significantly. This polarization effect is a powerful tool for astronomers to detect and measure stellar magnetic fields.

The Zeeman effect (Dutch: [ˈzeːmɑn]) is the splitting of a spectral line into several components in the presence of a static magnetic field. It is caused by the interaction of the magnetic field with the magnetic moment of the atomic electron associated with its orbital motion and spin; this interaction shifts some orbital energies more than others, resulting in the split spectrum. The effect is named after the Dutch physicist Pieter Zeeman, who discovered it in 1896 and received a Nobel Prize in Physics for this discovery. 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 forbidden (in the dipole approximation), as governed by the selection rules.

Since the distance between the Zeeman sub-levels is a function of magnetic field strength, this effect can be used to measure magnetic field strength, e.g. that of the Sun and other stars or in laboratory plasmas.

Discovery

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In 1896 Zeeman learned that his laboratory had one of Henry Augustus Rowland's highest resolving diffraction gratings. Zeeman had read James Clerk Maxwell's article in Encyclopædia Britannica describing Michael Faraday's failed attempts to influence light with magnetism. Zeeman wondered if the new spectrographic techniques could succeed where early efforts had not.[1]: 75 

When illuminated by a slit-shaped source, the grating produces a long array of slit images corresponding to different wavelengths. Zeeman placed a piece of asbestos soaked in salt water into a Bunsen burner flame at the source of the grating: he could easily see two lines for sodium light emission. Energizing a 10-kilogauss magnet around the flame, he observed a slight broadening of the sodium images.[1]: 76 

When Zeeman switched to cadmium as the source, he observed the images split when the magnet was energized. These splittings could be analyzed with Hendrik Lorentz's then-new electron theory. In retrospect, we now know that the magnetic effects on sodium require quantum-mechanical treatment.[1]: 77  Zeeman and Lorentz were awarded the 1902 Nobel Prize; in his acceptance speech Zeeman explained his apparatus and showed slides of the spectrographic images.[2]

Nomenclature

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Historically, one distinguishes between the normal and an anomalous Zeeman effect (discovered by Thomas Preston in Dublin, Ireland[3]). The anomalous effect appears on transitions where the net spin of the electrons is non-zero. 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. Wolfgang Pauli recalled that when asked by a colleague as to why he looked unhappy, he replied: "How can one look happy when he is thinking about the anomalous Zeeman effect?"[4]

At higher magnetic field strength the effect ceases to be linear. At even higher field strengths, comparable to the strength of the atom's internal field, the electron coupling is disturbed and the spectral lines rearrange. This is called the Paschen–Back effect.

In modern scientific literature, these terms are rarely used, with a tendency to use just the "Zeeman effect". Another rarely used obscure term is inverse Zeeman effect,[5] referring to the Zeeman effect in an absorption spectral line.

A similar effect, splitting of the nuclear energy levels in the presence of a magnetic field, is referred to as the nuclear Zeeman effect.[6]

Theoretical presentation

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The total Hamiltonian of an atom in a magnetic field is where is the unperturbed Hamiltonian of the atom, and is the 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 here. Therefore, where is the Bohr magneton, is the total electronic angular momentum, and is the Landé 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 contributions of the orbital angular momentum and the spin angular momentum , with each multiplied by the appropriate gyromagnetic ratio: where , and (the anomalous gyromagnetic ratio, deviating from 2 due to the effects of quantum electrodynamics). In the case of the LS coupling, one can sum over all electrons in the atom: where and are the total spin 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 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, exceeds the LS coupling significantly (but is still small compared to ). In ultra-strong magnetic fields, the magnetic-field interaction may exceed , in which case the atom can no longer exist in its normal meaning, and one talks about Landau levels instead. There are intermediate cases that are more complex than these limit cases.

Weak field (Zeeman effect)

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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 and using and squaring both sides, we get

Combining everything and taking , we obtain the magnetic potential energy of the atom in the applied external magnetic field: where the quantity in square brackets is the Landé g-factor of the atom ( ), and is the z component of the total angular momentum.

For a single electron above filled shells, with and , the Landé g-factor can be simplified to

Taking to be the perturbation, the Zeeman correction to the energy is

Example: Lyman-alpha transition in hydrogen

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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 and levels into 2 states each () and the level into 4 states (). The Landé 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. Fine-structure 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.

Dipole-allowed Lyman-alpha transitions in the weak-field regime
Initial state

Final state

Energy
perturbation

Strong field (Paschen–Back effect)

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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 strong to disrupt the coupling between orbital () and spin () angular momenta. This effect is the strong-field limit of the Zeeman effect. When , the two effects are equivalent. The effect was named after the German physicists Friedrich Paschen and Ernst E. A. Back.[7]

When the magnetic-field perturbation significantly exceeds the spin–orbit interaction, one can safely assume . This allows the expectation values of and to be easily evaluated for a state . The energies are simply

The above may be read as implying that the LS-coupling is completely broken by the external field. However, and 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 is independent of the unperturbed energies and electronic configurations of the levels being considered.

More precisely, if , each of these three components is actually a group of several transitions due to the residual spin–orbit coupling and relativistic corrections (which are of the same order, known as 'fine structure'). The first-order perturbation theory with these corrections yields the following formula for the hydrogen atom in the Paschen–Back limit:[8]

Example: Lyman-alpha transition in hydrogen

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In this example, the fine-structure corrections are ignored.

Dipole-allowed Lyman-alpha transitions in the strong-field regime
Initial state

()

Initial energy perturbation Final state

()

Final energy perturbation

Intermediate field for j = 1/2

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In the magnetic dipole approximation, the Hamiltonian which includes both the hyperfine and Zeeman interactions is[citation needed]

where is the hyperfine splitting at zero applied magnetic field, and are the Bohr magneton and nuclear magneton, respectively (note that the last term in the expression above describes the nuclear Zeeman effect), and are the electron and nuclear angular momentum operators and is the Landé g-factor:

In the case of weak magnetic fields, the Zeeman interaction can be treated as a perturbation to the basis. In the high field regime, the magnetic field becomes so strong that the Zeeman effect will dominate, and one must use a more complete basis of or just since and will be constant within a given level.

To get the complete picture, including intermediate field strengths, we must consider eigenstates which are superpositions of the and basis states. For , the Hamiltonian can be solved analytically, resulting in the Breit–Rabi formula (named after Gregory Breit and Isidor Isaac Rabi). Notably, the electric quadrupole interaction is zero for (), so this formula is fairly accurate.

We now utilize quantum mechanical ladder operators, which are defined for a general angular momentum operator as

These ladder operators have the property

as long as lies in the range (otherwise, they return zero). Using ladder operators and We can rewrite the Hamiltonian as

We can now see that at all times, the total angular momentum projection will be conserved. This is because both and leave states with definite and unchanged, while and either increase and decrease or vice versa, so the sum is always unaffected. Furthermore, since there are only two possible values of which are . Therefore, for every value of there are only two possible states, and we can define them as the basis:

This pair of states is a two-level quantum mechanical system. Now we can determine the matrix elements of the Hamiltonian:

Solving for the eigenvalues of this matrix – as can be done by hand (see two-level quantum mechanical system), or more easily, with a computer algebra system – we arrive at the energy shifts:

where is the splitting (in units of Hz) between two hyperfine sublevels in the absence of magnetic field , is referred to as the 'field strength parameter' (Note: for the expression under the square root is an exact square, and so the last term should be replaced by ). This equation is known as the Breit–Rabi formula and is useful for systems with one valence electron in an () level.[9][10]

Note that index in should be considered not as total angular momentum of the atom but as asymptotic total angular momentum. It is equal to total angular momentum only if otherwise eigenvectors corresponding different eigenvalues of the Hamiltonian are the superpositions of states with different but equal (the only exceptions are ).

Applications

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Astrophysics

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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,[11] and to analyze the magnetic field geometries in other stars.[12]

Laser cooling

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The Zeeman effect is utilized in many laser cooling applications such as a magneto-optical trap and the Zeeman slower.[13]

Spintronics

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Zeeman-energy mediated coupling of spin and orbital motions is used in spintronics for controlling electron spins in quantum dots through electric dipole spin resonance.[14]

Metrology

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Old high-precision frequency standards, i.e. hyperfine structure transition-based atomic clocks, may require periodic fine-tuning due to exposure to magnetic fields. This is carried out by measuring the Zeeman effect on specific hyperfine structure transition levels of the source element (cesium) and applying a uniformly precise, low-strength magnetic field to said source, in a process known as degaussing.[15]

The Zeeman effect may also be utilized to improve accuracy in atomic absorption spectroscopy.[citation needed]

Biology

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A theory about the magnetic sense of birds assumes that a protein in the retina is changed due to the Zeeman effect.[16]

Nuclear spectroscopy

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The nuclear Zeeman effect is important in such applications as nuclear magnetic resonance spectroscopy, magnetic resonance imaging (MRI), and Mössbauer spectroscopy.[citation needed]

Other

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The electron spin resonance spectroscopy is based on the Zeeman effect.[citation needed]

Demonstrations

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Diagram of a Zeeman effect demonstration

The Zeeman effect can be demonstrated by placing a sodium vapor source in a powerful electromagnet and viewing a sodium vapor lamp through the magnet opening (see diagram). With magnet off, the sodium vapor source will block the lamp light; when the magnet is turned on the lamp light will be visible through the vapor.

The sodium vapor can be created by sealing sodium metal in an evacuated glass tube and heating it while the tube is in the magnet.[17]

Alternatively, salt (sodium chloride) on a ceramic stick can be placed in the flame of Bunsen burner as the sodium vapor source. When the magnetic field is energized, the lamp image will be brighter.[18] However, the magnetic field also affects the flame, making the observation depend upon more than just the Zeeman effect.[17] These issues also plagued Zeeman's original work; he devoted considerable effort to ensure his observations were truly an effect of magnetism on light emission.[19]

When salt is added to the Bunsen burner, it dissociates to give sodium and chloride. The sodium atoms get excited due to photons from the sodium vapour lamp, with electrons excited from 3s to 3p states, absorbing light in the process. The sodium vapour lamp emits light at 589nm, which has precisely the energy to excite an electron of a sodium atom. If it was an atom of another element, like chlorine, shadow will not be formed.[20][failed verification] When a magnetic field is applied, due to the Zeeman effect the spectral line of sodium gets split into several components. This means the energy difference between the 3s and 3p atomic orbitals will change. As the sodium vapour lamp don't precisely deliver the right frequency anymore, light doesn't get absorbed and passes through, resulting in the shadow dimming. As the magnetic field strength is increased, the shift in the spectral lines increases and lamp light is transmitted.[citation needed]

See also

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References

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Revisions and contributorsEdit on WikipediaRead on Wikipedia
from Grokipedia
The Zeeman effect is a physical phenomenon in which the spectral lines emitted or absorbed by atoms or molecules in a magnetic field are split into multiple closely spaced components, revealing the influence of the field on atomic energy levels. Discovered in 1896 by Dutch physicist Pieter Zeeman at Leiden University, the effect was first observed as a broadening and subsequent resolution into distinct lines in the emission spectra of elements like sodium and cadmium when exposed to a magnetic field generated by an electromagnet. This observation provided early experimental evidence for the existence of charged subatomic particles, as the splitting patterns allowed for the determination of the electron's charge-to-mass ratio shortly before J.J. Thomson's formal discovery of the electron in 1897. Theoretical insight into the Zeeman effect came rapidly from Hendrik Lorentz, Zeeman's mentor, who in 1897 explained the splitting and polarization of the lines using his electron model of the atom, predicting a triplet structure for certain transitions under weak fields. For their combined contributions to understanding the connection between magnetism and radiation, Lorentz and Zeeman shared the 1902 Nobel Prize in Physics. The effect manifests in two primary forms: the normal Zeeman effect, seen in spectral lines involving transitions without electron spin (such as singlet states in multi-electron atoms), where a line splits into three components—one unshifted π line parallel to the field and two symmetrically shifted σ lines perpendicular to it, with the σ components exhibiting circular polarization. The more prevalent anomalous Zeeman effect produces irregular multiplets due to the additional influence of electron spin, which couples with orbital angular momentum to create a total angular momentum that interacts with the external field. In quantum mechanical terms, the external magnetic field lifts the degeneracy of atomic states labeled by the magnetic quantum number, causing energy shifts proportional to the Bohr magneton μ_B, the field strength B, and the Landé g-factor, as ΔE = μ_B B m_j g_L. Beyond fundamental atomic physics, the Zeeman effect has significant applications in spectroscopy and astrophysics, enabling precise measurements of magnetic fields in stellar atmospheres and the Sun's corona through the analysis of line splitting and Stokes polarization parameters in observed spectra. For instance, it has been used to map solar magnetic fields with resolutions down to kilogauss strengths and to probe magnetic fields in star-forming regions, confirming their role in regulating star formation processes.

Historical Background

Discovery and Early Observations

The Zeeman effect was first observed in 1896 by Dutch physicist Pieter Zeeman at Leiden University, where he noted the broadening of spectral lines emitted by a sodium flame when subjected to a magnetic field. Working under the supervision of Hendrik Lorentz, Zeeman conducted these experiments amid ongoing scientific debates regarding the ether drift and the electromagnetic nature of light, as explored in Lorentz's theories. His setup involved placing the light source—a flame containing sodium or other elements—between the poles of a powerful electromagnet, allowing for controlled application of magnetic fields to the emitting atoms. Using a high-resolution Rowland grating spectrometer, Zeeman analyzed the emitted light in two primary configurations: transverse, where the magnetic field was perpendicular to the observation direction, and longitudinal, where it was parallel. In the transverse setup, the normally sharp spectral lines broadened and, upon closer inspection with improved resolution, split into three or more polarized components, revealing distinct shifts in wavelength. The longitudinal observations similarly showed splitting, but with circular polarization in the separated lines, indicating the field's directional influence on light emission. These findings extended to other elements like cadmium, confirming the phenomenon's generality. Zeeman's initial quantitative measurements revealed a splitting of approximately 0.01 nm for the sodium D-lines under magnetic fields of about 1 T, marking a subtle but measurable effect that required precise instrumentation to detect. He first communicated these results to the Royal Academy of Sciences in Amsterdam on October 31, 1896, in a paper titled "Over den invloed eener magnetisatie op den aard van het door een stof uitgezonden licht." The discovery garnered immediate international attention, with further publications in 1897 detailing resolved splittings in cadmium spectra. This work led to Zeeman sharing the 1902 Nobel Prize in Physics with Hendrik Lorentz, recognized for their joint contributions to understanding magnetism's influence on radiation. Lorentz offered a classical interpretation of the effect based on the perturbation of charged particle orbits in atoms by the magnetic field.

Theoretical Explanations and Nomenclature

Following the experimental discovery, Hendrik Lorentz developed a classical theoretical model in 1897 to explain the observed spectral line splitting. In this model, Lorentz attributed the phenomenon to the Larmor precession of charged electron orbits within atoms under the influence of an external magnetic field, which modulates the emitted light frequencies and predicts a triplet splitting for spectral lines arising from transitions without electron spin considerations. This classical approach successfully described the simplest case but failed to account for more complex splittings in multi-electron atoms. The nomenclature for the Zeeman effect evolved from Zeeman's initial description of it as a "magneto-optic phenomenon" in his 1896–1897 publications, reflecting its connection to earlier magneto-optical studies. The terms "normal Zeeman effect" and "anomalous Zeeman effect" were later introduced to distinguish between the classical prediction and unexplained observations: the normal effect refers to the splitting of singlet spectral lines into three components (a triplet), consistent with Lorentz's theory, while the anomalous effect describes the irregular multiplet patterns seen in spectral lines from atoms exhibiting electron spin-orbit interactions, which deviated from classical expectations. These terms, coined around 1912 by Friedrich Paschen and Ernst Back in their studies of magnetic field effects on spectra, highlighted the limitations of classical physics and spurred quantum developments. Early quantum efforts to resolve these discrepancies began with Arnold Sommerfeld's 1916 extension of the Bohr model, introducing additional quantum numbers to link the splitting patterns to the orbital angular momentum LL and an inner quantum number associated with spin-like behavior, though without a full physical interpretation. In the early 1920s, Alfred Landé developed a vector model for atomic angular momentum, deriving the Landé g-factor that empirically accounted for the anomalous splittings without invoking electron spin. The anomalous effect was ultimately explained in 1925 by George Uhlenbeck and Samuel Goudsmit through their hypothesis of electron spin, proposing that electrons possess an intrinsic angular momentum S=12S = \frac{1}{2} \hbar in addition to orbital angular momentum LL, leading to a total angular momentum J=L+S\mathbf{J} = \mathbf{L} + \mathbf{S} that governs the splitting via magnetic interactions. Key quantities in these explanations include the atomic magnetic moment μ\mu, often expressed in units of the Bohr magneton μB=e2me\mu_B = \frac{e \hbar}{2 m_e}, where ee is the elementary charge, \hbar is the reduced Planck's constant, and mem_e is the electron mass. The characteristic Larmor frequency of precession is given by ωL=eB2me\omega_L = \frac{e B}{2 m_e}, with BB the magnetic field strength, directly relating the energy shift to the field in classical and early quantum treatments.

Theoretical Framework

Hamiltonian Formulation

The quantum mechanical description of the Zeeman effect begins with the total Hamiltonian for an atomic system in an external magnetic field, given by H=H0+HZH = H_0 + H_Z, where H0H_0 is the unperturbed atomic Hamiltonian encompassing the kinetic energy, Coulomb interactions, and possibly fine structure corrections, while HZH_Z represents the interaction between the atomic magnetic moment and the magnetic field./06%3A_Perturbative_Approaches/6.04%3A_The_Zeeman_Effect) This formulation assumes a non-relativistic framework and a uniform magnetic field B\vec{B}
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