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Alfred Landé organized the magnetic response of coupled atomic angular momenta. The Landé g-factor relates a magnetic energy shift to the projection of total angular momentum, accounting for both orbital angular momentum and spin. For LS coupling, $g_J=1+[J(J+1)+S(S+1)-L(L+1)]/[2J(J+1)]$ when $J\ne 0$, neglecting the small correction to the electron spin g-factor. For $L=0$ and $J=S=1/2$, it gives $g_J=2$. Different atomic terms therefore split differently in a weak magnetic field.^[ref]

A physicist.^[ref]

An LS coupling multiplet with specified total orbital angular momentum $L$ and total spin $S$, usually within a specified electron configuration. Its magnetic states have $M_L=-L,\dots ,L$ and $M_S=-S,\dots ,S$. Spin-orbit coupling splits it into atomic fine-structure levels.

Friedrich Hund's rules describe the usual ground-term ordering within an atomic electron configuration in the LS coupling regime. First maximize the total spin $S$ subject to the Pauli exclusion principle. Among the terms with that spin, maximize total orbital angular momentum $L$. Within the resulting term, the lowest level has $J=|L-S|$ for a less-than-half-filled open subshell and $J=L+S$ for a more-than-half-filled one. These are ordering rules, not universal replacements for diagonalizing an arbitrary atomic Hamiltonian operator.

For two equivalent $p$ electrons, parallel spins give $S=1$. Their spatial wavefunction must be antisymmetric; the highest allowed orbital projection with parallel spins is $1+0=1$, giving $L=1$. A $p^2$ subshell is less than half filled, so its lowest term symbol is ${}^3{P}_0$, followed within that term by ${}^3{P}_1$ and ${}^3{P}_2$. Closed subshells contribute zero total $L$ and $S$.

Polykarp Kusch and Henry Michael Foley compared hyperfine structure resonance frequencies for different electronic states of gallium, indium and sodium. Their 1948 paper reports mutually consistent departures from the ratios expected with orbital factor $1$ and spin factor $2$. Comparing several states constrained the alternative explanation of perturbed atomic levels.^[ref]

The Rabi molecular beam magnetic resonance experiment explains the readout principle: a resonant transition changes an atom's magnetic response, and hence its transmitted beam signal. Kusch describes rapidly interchangeable ovens, several radio frequency oscillators and careful field homogenization. Measurements taken during monotonic field drift were reduced to a common field.^[ref]

Real hyperfine structure lines are not simply bare electronic $g_J$ times field. Nuclear magnetic moments, known interaction constants and nonlinear field dependence enter the inference.^[ref] Field homogeneity controls line broadening; alternating species addresses drift. Neither control removes an error in the atomic model. The beauty of the comparison is the separation of two problems: cancelling a shared calibration scale and testing whether several physical systems imply the same electron spin g-factor.

The closed shells have $L=S=0$, so only the two equivalent p electrons matter. Their addition of angular momentum allows $L=0,1,2$ and $S=0,1$, subject to the Pauli exclusion principle. Interchanging two $l=1$ orbital states has sign $(-1{)}^{2-L}=(-1{)}^L$: even L is spatially symmetric and needs the antisymmetric spin singlet; odd L is spatially antisymmetric and needs the symmetric spin triplet. Thus the allowed LS terms of a p-squared configuration are ${}^{1}S$, ${}^{1}D$ and ${}^{3}P$.

In LS coupling, $J=|L-S|,\dots ,L+S$. The complete list of term symbols is thereforeThey contain $1+5+(1+3+5)=15=\left(\genfrac{}{}{0ex}{}{6}{2}\right)$ magnetic substates, exhausting the antisymmetric two-electron space. All have even spatial parity, since each p orbital is odd.

The printed magnetic dipole moment uses dimensionless angular momentum operators: their physical counterparts are $\hslash \mathbf{L}$ and $\hslash \mathbf{S}$. Choose the magnetic field along $z$. Then the Zeeman energy is $H_Z={\mu }_{B}B(L_z+g_s{S}_z)$, whose characteristic size is ${\mu }_{B}B$. In LS coupling, treating this as a time-independent perturbation theory requires it to be much smaller than the relevant fine structure separation, rather than merely smaller than the Coulomb interaction energy.

For a concrete hydrogen atom estimate take the $2p_{1/2},2p_{3/2}$ pair. The hydrogen fine-structure correction iswhere ${\alpha }_{\mathrm{fs}}$ is the fine-structure constant, distinguished from the later potential coefficient. ThusConsequently a suitable weak-magnetic field condition for this pair isThere is no single threshold for every hydrogen energy level: the relevant fine structure separations decrease with $n$. The $1s$ energy level has no same-$n$ spin-orbit interaction partner, so it cannot itself define this comparison. This calculation neglects hyperfine structure; resolving that smaller scale requires an additional weak-magnetic field condition.

The closed $1s^{2}2s^2$ shells have $L=S=0$, leaving the equivalent $2p^2$ electrons. Addition of angular momentum and the Pauli exclusion principle permit the atomic terms ${}^{3}P,{}^{1}D,{}^{1}S$. Their term symbols use ${}^{2S+1}{L}_J$. Hund's rules put the triplet state below the singlet states; for a less-than-half-filled $p$ shell the smallest $J$ in ${}^{3}P$ is lowest. ThusAll have even parity. These assignments agree with independent tabulated carbon energy levels.^[ref] The rounded source values should not be forced to satisfy an exact Landé interval rule; pure first-order LS coupling need not account for every measured fine structure correction.

In LS coupling, first add the individual orbital angular momenta and spins separately, then add their totals:The Coulomb interaction between electrons must separate different atomic terms more strongly than the spin-orbit interaction mixes them. Then $L,S,J,M_J$ are useful quantum numbers, with $J=|L-S|,\dots ,L+S$. This approximation is usually better for lighter chemical atoms and well-separated atomic terms; strong configuration interaction or strong spin-orbit coupling can spoil it. The term symbol is ${}^{2S+1}{L}_J$.

The general electric-dipole selection rules, for isolated chemical atoms with definite parity and total electronic angular momentum, are a change of parity, $\Delta J=0,\pm 1$ excluding $J=0\leftrightarrow 0$, and $\Delta M_J=0,\pm 1$, with the accessible magnetic sublevels determined by the light's polarization. In pure LS coupling, the additional selection rules are $\Delta S=0$ and $\Delta L=0,\pm 1$, excluding $L=0\leftrightarrow 0$. In a one-electron description the electric dipole operator also requires $\Delta l=\pm 1$ for the active electron. These latter statements can fail as exact labels when atomic terms mix; the general parity and total-angular momentum restrictions still apply. Unresolved hyperfine structure is neglected here.

For strontium, the closed core contributes $L=S=0$. The Pauli exclusion principle makes the two equivalent $5s$ electrons a singlet state. Different radial orbitals permit both a singlet state and a triplet state. Thus the complete lists of atomic fine-structure levels areThe $5s5p$ electron configuration has odd parity; the other two electron configurations have even parity.

For $5s5d$, addition of angular momentum gives $L=2$ and $S=0,1$. The even-parity atomic terms and atomic fine-structure levels areThe electric-dipole selection rules exclude all connections to the even-parity $5s^2$ and $5s6s$ electron configurations. To the odd-parity $5s5p$ electron configuration, all seven allowed connections in pure LS coupling areHere a connection is listed independently of whether the $5s5d$ energy level is above or below its partner.

In a weak magnetic field, use the Landé g-factorFor the three ${}^3{D}_J$ energy levels, this gives $1/2,7/6,4/3$; for ${}^3{P}_1,{}^3{P}_2$ it gives $3/2$. The six-component spectral line is thereforeA component has frequency displacement $({\mu }_{B}B/h)(m_D/2-3m_P/2)$. The electric dipole transition with $m_D=m_P=0$ has zero matrix element, since the relevant $J=1\leftrightarrow 1$ rank-one Clebsch-Gordan coefficients vanish there. The remaining allowed pairs giveThus all six frequency positions $\pm 1/2,\pm 1,\pm 3/2$ are distinct. Perpendicular to the magnetic field, both the $\pi$ and $\sigma$ components are visible, with mutually perpendicular linear polarizations. Along the magnetic field the $\pi$ components disappear. This is the weak-field Zeeman effect, before the Paschen-Back effect changes the coupling scheme.

Let the dimensionful angular momentum operators obey $\mathbf{F}=\mathbf{I}+\mathbf{J}$ and take the interaction Hamiltonian as $H^{\prime }=A\mathbf{I}\cdot \mathbf{J}$. Sincethe energy eigenvalues at fixed $I,J$ arewhere $F=|I-J|,\dots ,I+J$. Subtraction gives the Landé interval ruleMany atomic conventions use dimensionless angular momentum operators and call the energy-valued constant itself $A$; then the right-hand side is $AF$. Each energy level has $2F+1$ magnetic sublevels with the same energy in zero field.

For fine structure, the effective interaction is $a_{LS}\mathbf{L}\cdot \mathbf{S}$ with dimensionless angular momentum operators. It originates in the spin-orbit interaction, including the magnetic interaction of electron spin with orbital motion and its relativistic correction. Within an isolated LS coupling atomic term, the labels are the electron configuration, $L,S,J,M_J$, and the interval between adjacent $J$ energy levels is $a_{LS}J$. This is smaller than the electrostatic separation of atomic terms.

For magnetic-dipole hyperfine structure, the nuclear magnetic dipole moment interacts with the magnetic field generated by the electrons. Contributions include the Fermi contact interaction of penetrating $s$ electrons, orbital magnetic fields, and the dipolar field of electron spin. Projected onto one electronic $J$ energy level, their rotationally invariant magnetic-dipole part has the form $a_{IJ}\mathbf{I}\cdot \mathbf{J}$. The labels are $I,J,F,M_F$, together with the approximate electronic labels such as $L,S$. This splitting is generally smaller than fine structure, reflecting the much smaller nuclear magnetic dipole moment. An electric nuclear quadrupole moment can add a different interaction and violate the simple Landé interval rule.

At the larger electrostatic energy scale, an effective two-spin exchange interaction can also be written $a_s{\mathbf{s}}_1\cdot {\mathbf{s}}_2$ within fixed orbitals. Its origin is the Coulomb interaction combined with the Pauli exclusion principle, rather than a large direct magnetic interaction. It separates singlet state and triplet state atomic terms; before spin-orbit coupling, useful labels include the electron configuration, $L,M_L,S,M_S$. General electrostatic atomic term separations need not obey a single Landé interval rule as $L$ varies.

An electric dipole transition has amplitude proportional to $⟨f|\mathbf{d}\cdot \mathbf{ϵ}|i⟩$. The electric dipole operator is odd under parity, so the initial and final states must have opposite parity. As a rank-one spherical tensor it also requires $\Delta J=0,\pm 1$, excluding $J=0\leftrightarrow 0$, and $\Delta m_J=0,\pm 1$. These follow from angular-momentum addition and the Wigner-Eckart theorem; vanishing Clebsch-Gordan coefficients can impose further restrictions. Relative to the quantization axis, $\pi$ polarization drives $\Delta m=0$, while ${\sigma }^{\pm }$ drive $\Delta m=\pm 1$.

For a single active electron, parity and the orbital triangle rule combine to give $\Delta l=\pm 1$. In LS coupling, the spin-independent electric dipole operator gives $\Delta S=0$ and $\Delta L=0,\pm 1$, excluding $L=0\leftrightarrow 0$; total parity must still change. Spin-orbit mixing can weakly relax the approximate spin rule. For resolved hyperfine states the corresponding triangle rule is $\Delta F=0,\pm 1$, excluding $F=0\leftrightarrow 0$, with $\Delta m_F=0,\pm 1$. These labels require the appropriate coupling regime. There is no universal E1 rule demanding a particular change in principal quantum number. An E1-forbidden line may occur through another multipole or a multiphoton process.

In LS coupling, add all orbital and spin angular momenta separately:The quantum numbers specifyThus $M_L=-L,\dots ,L$ and $M_S=-S,\dots ,S$. The addition of angular momentum rule givesIn a product basis with individual projection labels,The magnitudes $L$ and $S$ are not generally the arithmetic sums of the individual magnitudes; they result from angular-momentum coupling. The sum rules for projections remain valid for every product component of a coupled angular momentum eigenstate.

Within a specified electron configuration in the LS coupling regime, Hund's rules select the lowest atomic term as follows. First maximize the total electron spin $S$ subject to the Pauli exclusion principle. Among the terms having that $S$, choose the largest total orbital angular momentum $L$. Finally, spin-orbit coupling places the smallest allowed $J=|L-S|$ lowest for a subshell less than half full, and the largest $J=L+S$ lowest for a subshell more than half full. At half filling the maximum-spin term has $L=0$, hence $J=S$. These rules rank terms within configurations; the exceptional neutral-atom configurations of chromium and copper must also be used.

For a fixed open-shell electron configuration in the LS coupling regime, Hund's rules select the free-ion ground term in the following order:

The first two rules come from the Coulomb interaction between electrons within the partially filled subshell, including its exchange interaction. Parallel spins require an antisymmetric spatial wavefunction, reducing close approach and often lowering the repulsive Coulomb interaction energy. Among the allowed high-spin terms, the angular dependence of the Coulomb interaction generally favours the largest $L$; a simple magnetic alignment argument alone does not derive this second ordering rule.

The weaker spin-orbit coupling then splits a selected $L,S$ term. In LS coupling, its term-level energy is proportional toThe effective sign appropriate to less-than-half versus more-than-half filling gives the third rule. These rules assume the electrostatic term separation dominates spin-orbit coupling; strong crystal field splitting or other coupling regimes require further analysis.

Potassium has a closed 18-electron core and one valence electron. In $3d{}^2{D}_{5/2}$ the orbital label specifies principal quantum number $n=3$ and single-electron orbital angular momentum $l=2$. The term letter D specifies total orbital angular momentum $L=2$, the superscript $2S+1=2$ specifies $S=1/2$, and the subscript is total electronic angular momentum $J=5/2$. The $5p{}^2{P}_{3/2}$ state instead has $n=5$, $l=L=1$, the same spin, and $J=3/2$. The closed electron shell that forms the core contributes no net $L$ or $S$ in this alkali-like approximation. The dash identifies a pair of levels rather than by itself specifying the direction of emission.

The leading electric dipole transition rules for one active electron areThe electronic parity must change, since the electric dipole operator is odd under spatial reflection. The electric-dipole selection rule imposes no general restriction on changing $n$ by more than one. The rule for magnetic sublevels depends on the radiation's polarization relative to the quantization axis: the $q=0$ component couples equal $m_J$, whereas $q=\pm 1$ supplies the other changes. In a many-electron description using LS coupling the total orbital rule is $\Delta L=0,\pm 1$, excluding $L=0\leftrightarrow 0$; for a single active electron the stronger $\Delta l=\pm 1$ applies. Thus the displayed D–P pair satisfies the leading rules. Relativistic mixing and higher-multipole transitions can permit weaker lines outside the approximation of electric dipole transitions.

For two valence electrons, the central-field shell structure should be the largest scale, residual electrostatic interactions should establish a reasonably definite configuration and atomic term, and spin-orbit coupling should be weaker than the separations between the relevant terms. Then $L$ and $S$ remain approximately good quantum numbers. Within a well-isolated term the leading fine structure interaction can be represented as $A\mathbf{L}\cdot \mathbf{S}$. Its coefficient must be effectively constant for all $J$ levels in that term. Mixing of neighboring terms, spin-spin interactions, higher-order corrections or strong applied fields can spoil the simple interval rule; hyperfine structure must be negligible or separately resolved.

A suitable approximate example is the magnesium $3s3p{}^3{P}_J$ term, with $L=1$, $S=1$ and $J=0,1,2$. The interval-rule prediction isAn arbitrary common term energy may be added. For $A>0$ the levels ascend in the order ${}^3{P}_0,{}^3{P}_1,{}^3{P}_2$, with gap ratio one to two. Each level still contains $2J+1$ degenerate magnetic sublevels in zero external field. The superscript three labels the spin multiplicity $2S+1$, while the different subscripts identify fine structure components of that same term. This is an approximate example of LS coupling, not a claim that every real two-electron atom has exact one-to-two fine splitting.

Within a fixed isolated electronic $J$ multiplet, the electronic field at the nucleus is a vector operator. Rotational symmetry and the Wigner-Eckart theorem imply that its projection into this multiplet is proportional to $\mathbf{J}$:Its detailed orbital, spin-dipolar and contact contributions are included in the reduced coefficient $b_J$. Consequently the projected magnetic-dipole hyperfine interaction becomesin the same dimensionless angular-momentum convention as a. The proportionality is a statement about matrix elements within the chosen electronic manifold, not an identity for the electron field operator on the entire atomic Hilbert space.

Define $\mathbf{F}=\mathbf{I}+\mathbf{J}$. In zero external field the quantum states obtained by addition of angular momentum are labelled $|\gamma J,I;F,m_F⟩$, where $\gamma$ specifies the electron configuration and other fixed labels. The good quantum numbers include $I,J,F,m_F$, with $F=|I-J|,\dots ,I+J$ and $m_F=-F,\dots ,F$. In a description using LS coupling the fixed electronic labels can also include $L,S$. The energies depend on $F$ but not $m_F$:This neglects coupling to other electronic manifolds, electric-quadrupole hyperfine interactions and the Zeeman effect from external fields. Those additions can shift the intervals or change which quantum numbers remain useful.

For the electronic ${}^2{S}_{1/2}\to {}^2{P}_{1/2}$ transition, neglect hyperfine structure and use weak-field LS coupling. The Landé g-factors are $g_g=2$ and $g_e=2/3$, so a transition from $m_g$ to $m_e$ shifts by $({\mu }_{B}B/h)(g_e{m}_e-g_g{m}_g)$.

With propagation perpendicular to the magnetic field, linear polarization parallel to the field drives the $\pi$ electric-dipole selection rule $\Delta m=0$. The two shifts are $\pm 2{\mu }_{B}B/(3h)$. Perpendicular linear polarization is an equal-amplitude combination of the two field-axis circular components, driving ${\sigma }^{\pm }$ transitions with $\Delta m=\pm 1$ and shifts $\pm 4{\mu }_{B}B/(3h)$. Each geometry therefore selects a doublet, with twice the separation in the perpendicular-polarization case. Equal line heights within a pair require equal lower-state populations and an unsaturating probe; line positions do not require that extra population assumption.

A chemical element of atomic number 59. Its trivalent ion has a $4f^2$ open-shell electron configuration. In LS coupling, Hund's rules select $L=5$, $S=1$, $J=4$, the ${}^3{H}_4$ term symbol. The corresponding free-ion Landé g-factor is $4/5$ and its effective paramagnetic moment is $(4/5)\sqrt{20}{\mu }_B\simeq 3.58{\mu }_B$.

An original reduced model makes the cancellation explicit. Assume LS coupling, neglect nuclear spin, and write the electronic magnetic dipole moment as $-{\mu }_B(g_L\mathbf{L}+g_s\mathbf{S})/\hslash$. For $L=1$, $S=1/2$, the projection used to derive the Landé g-factor givesThese coefficients follow by substituting $J=3/2$ or $1/2$ into the angular-momentum projection formula; neither level measures pure spin alone. In a weak uniform magnetic field, adjacent electronic projections have spacing $h{f}_J=g_J{\mu }_{B}B$ when $g_J>0$. ThereforeThe common magnetic field and Bohr magneton cancel. The ratio determines $g_s/g_L$, not $g_s$ without further knowledge of $g_L$. For $g_L=1$, it gives $a_e=(R-2)/(R+1)$. Small departures from $R=2$ are magnified differently from small departures of $g_s$ from $2$; the two fractional changes should not be identified.

With the stipulated inputs $g_L=1$, $g_s=2.0024$ and ${\mu }_{B}B/h=100\mathrm{MHz}$, the two electronic frequencies are $66.5867$ and $133.4133\mathrm{MHz}$. Their ratio is approximately $2.0036043$, and inversion recovers $a_e=0.0012$. These are ideal electronic lines, not historical gallium data. Nuclear spin, mixing between levels and other deviations from LS coupling require a more complete model in an actual atom.