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The anomalous Zeeman effect is Zeeman splitting whose pattern is not the simple orbital triplet. Spin and spin-orbit interaction make the upper and lower Landé g-factors differ. The same weak-field formula still applies when its assumptions hold: “anomalous” does not mean nonlinear in the magnetic field.

For example, take an electronic transition with $L_u=1,S_u=1/2,J_u=1/2$ and $L_l=0,S_l=1/2,J_l=1/2$, neglecting hyperfine structure. With $g_s=2$, the formula above gives $g_u=2/3$ and $g_l=2$. The two allowed $q=0$ transitions have dimensionless shifts $g_u{m}_u-g_l{m}_l=\pm 2/3$, while the $q=\pm 1$ transitions give $\pm 4/3$. Thus there are four frequencies, even though each level contains only two magnetic quantum numbers. This is an independent worked deduction; it should not be substituted for the unresolved widths in the 1896 experiment.

Choose the one-particle states of a hydrogen atom, or a central-field description of a chemical atom, with labelsThe principal quantum number $n$ identifies the electron shell. The orbital angular momentum label $\ell$ identifies the electron subshell; the magnetic quantum number $m_{\ell }$ labels $2\ell +1$ independent spatial orbitals. Each has two spin one-half along an axis choices, hence $2(2\ell +1)$ spin orbitals. Applying the Pauli exclusion principle once per spin orbital givesThese quantum numbers label wavefunctions and spin projections, not electron trajectories. They need not resolve exact energy eigenstates in the presence of spin-orbit interaction; changing to coupled angular momentum eigenstates preserves the count of independent one-particle states within this shell model.

For example, $n=3$ allows $\ell =0,1,2$, conventionally $3s,3p,3d$. Their spatial orbital counts are $1,3,5$; their spin orbital counts are $2,6,10$. The sum is eighteen. The algebra behind “one per complete state” is short: two-particle antisymmetrization gives $u\wedge u=(u\otimes u-u\otimes u)/\sqrt{2}=0$, and the zero vector cannot be a normalized quantum state. Opposite-spin electrons in the same spatial orbital have distinct complete states, so their antisymmetric product survives.

This supplies a structural link to the periodic table: finite electron subshell capacities make repeated patterns of occupied electron configurations possible. It does not predict the exact ground state electron configuration or energy of a many-electron chemical atom. Different electron subshells overlap in energy, and electron interactions change their ordering. In particular, the periodic table period lengths are not simply successive $2n^2$ values: the third periodic table period has eight chemical elements, although the full $n=3$ electron shell has eighteen available states. A capacity counts available spin orbitals; an actual filling order requires a Quantum Hamiltonian.

The 1948 empirical synthesis preceded the 1949 strong spin-orbit interaction proposals. Johannes Hans Daniel Jensen recalled developing that idea in a discussion with colleagues, independently of Maria Goeppert Mayer's work; their shared problem was to account for the observed magic numbers and spins.^[ref]

Johannes Hans Daniel Jensen emphasized that even nuclear ground states retain correlations and that independent-particle motion becomes less adequate at higher excitation. This helps explain why the nuclear shell model needs residual interactions and complementary collective descriptions.^[ref]

The 1963 Nobel Prize in Physics recognized Maria Goeppert Mayer and Johannes Hans Daniel Jensen for nuclear shell structure. Eugene Paul Wigner's share recognized his contributions to nuclear and elementary-particle theory, especially fundamental symmetry principles, a distinct award motivation.^[ref]

For a point, fixed proton, the sum of the relativistic kinetic-energy correction, spin-orbit interaction including the Thomas precession factor, and Darwin term has the displayed leading correction. It depends on n and total angular momentum j, but not separately on l. Thus $2S_{1/2}$ and $2P_{1/2}$ remain degenerate while $2P_{3/2}$ lies above them. Radiative corrections, recoil, nuclear size and hyperfine structure require additional terms. The fine-structure constant is ${\alpha }_{\mathrm{fs}}=e^2/(4\pi {ϵ}_0\hslash c)$.

The splitting of one-nucleon energy levels by their spin-orbit interaction. With $\mathbf{J}=\mathbf{L}+\mathbf{S}$, the identity $2\mathbf{L}\cdot \mathbf{S}={\mathbf{J}}^2-{\mathbf{L}}^2-{\mathbf{S}}^2$ gives, in a state of definite $l,s=1/2,j$,The second branch requires $l\ge 1$. For the illustrative Hamiltonian operator $H_{\mathrm{so}}=-a\mathbf{L}\cdot \mathbf{S}/{\hslash }^2$ with $a>0$, the shifts are $-al/2$ and $+a(l+1)/2$. Thus the strong negative coefficient lowers the aligned $j=l+1/2$ branch. Its capacity is $2l+2$; the raised partner holds $2l$. Together they still hold $4l+2=2(2l+1)$ identical nucleons: the interaction rearranges states rather than creating them.

In this example the $d_{5/2}$ and $d_{3/2}$ shifts are $-a$ and $3a/2$, respectively, so the gap is $5a/2$. The capacity-weighted mean shift vanishes:This is a useful check on both the sign and state counting. A seventh identical particle cannot occupy another substate of the already full lower level. In a real atomic nucleus, other radial and orbital angular momentum levels can interleave with this doublet, and a radial coupling need not give the same effective $a$ for every orbital.

In the Paschen-Back effect, the external magnetic field interaction becomes large compared with the spin-orbit interaction that holds $\mathbf{L}$ and $\mathbf{S}$ coupled. Then $J$ ceases to be a good approximate quantum number; $m_L,m_S$ become more useful, with leading electronic shifts $\Delta E\simeq {\mu }_{B}B(m_L+g_s{m}_S)$. In the ideal complete-decoupling limit an electric-dipole interaction preserves $m_S$, so its spin contribution cancels between the levels and orbital triplet spacing can reappear. Intermediate fields require mixing the coupled states. This is a change of coupling regime, distinct from the weak-field anomalous Zeeman effect; still larger fields require additional terms beyond this linear model.

For a one-electron P-to-S transition with nuclear spin zero, ten electric-dipole sublevel channels have finite strength at weak nonzero field. Six retain finite strength in the complete orbital-spin decoupling limit. Channel count is distinct from spectral frequency count: retaining first-order residual spin-orbit interaction energy gives five distinct frequencies, with two central channels degenerate.

For a representative unstrained zinc blende structure III-V semiconductor such as gallium arsenide, take the valence-band maximum at the Gamma point as zero. The near-centre ordering is an s-like ${\Gamma }_{6c}$ conduction band doublet above a p-like ${\Gamma }_{8v}$ valence quartet. Spin-orbit interaction puts the p-like ${\Gamma }_{7v}$ doublet below the quartet by ${\Delta }_{\mathrm{so}}$. These are the zone-centre bands of a zinc-blende III-V semiconductor.

The $j=3/2$ quartet produces the heavy-hole and light-hole bands. Along a chosen symmetry direction, their components have $|m_j|=3/2$ and $1/2$ respectively; their different curvatures define different positive hole effective masses. They are degenerate at zero wavevector in the unstrained cubic crystal, but separate away from it. The $j=1/2$ doublet is the split-off valence band. To leading isotropic order,Valence-band curvature is negative for electrons; the corresponding hole masses are positive. Real valence bands warp with direction, so these are illustrative effective-mass parabolas rather than an exact spherical band structure.

The k·p perturbation theory couples the s-like and p-like states through momentum matrix elements. It controls the conduction-band mass, nonparabolicity and mixing of hole characters. Strain or quantum confinement can split the heavy/light degeneracy even at zero in-plane wavevector. The lack of inversion symmetry in zinc blende also permits spin splitting away from the zone centre; time-reversal symmetry still protects the zone-centre doublets.

The s–p electric-dipole transitions near $\Gamma$ are optically important and produce structures at $E_g$ and $E_g+{\Delta }_{\mathrm{so}}$ with polarization-dependent weights. For direct band gap compounds the conduction minimum is also at $\Gamma$, allowing near-edge absorption and emission without a momentum-supplying phonon. Not every III-V compound is direct-gap, and wurtzite materials have an additional crystal-field splitting; the cubic scheme should not be imposed on every III-V semiconductor. ^[ref]

For a point, stationary proton, the leading hydrogen fine structure comes from three order-$1/c^2$ contributions to the nonrelativistic electron Hamiltonian:These are the relativistic kinetic-energy correction, spin-orbit interaction and Darwin term. The spin-orbit coefficient includes the Thomas precession factor of one half; $⟨\mathbf{L}\cdot \mathbf{S}⟩={\hslash }^2[j(j+1)-l(l+1)-3/4]/2$. The Coulomb Darwin contribution is a positive contact term, relevant for S states. These corrections distinguish total angular momentum $j=l\pm 1/2$, while leaving magnetic substates degenerate without an external field.

Writing ${\alpha }_{\mathrm{fs}}=e^2/(4\pi {ϵ}_0\hslash c)$, the combined hydrogen fine-structure correction isThus the splitting is of order ${\alpha }_{\mathrm{fs}}^2$ times the principal binding energy. In the $n=2$ shell, $2S_{1/2}$ and $2P_{1/2}$ remain degenerate in this approximation, while $2P_{3/2}$ is higher by $m_e{c}^2{\alpha }_{\mathrm{fs}}^4/32$. The Lamb shift lifts the remaining S–P degeneracy; hyperfine structure is a separate nuclear-spin effect. Neither is part of the displayed correction. Nuclear recoil and finite nuclear size have also been neglected. ^[ref]

The Zeeman effect comes from $-\mathbf{\mu }\cdot \mathbf{B}$. For an electron, the orbital and spin magnetic moments are approximately $-{\mu }_B\mathbf{L}/\hslash$ and $-2{\mu }_B\mathbf{S}/\hslash$, respectively. This explains both the sign and the relative factor two in the term linear in $B$. The second term is the spin-orbit interaction: the electron's motion through the atomic electric field produces a magnetic interaction in its rest frame. The relativistic correction, including Thomas precession, and the radial expectation value are incorporated into $K$. This effective Hamiltonian retains the linear Zeeman splitting and spin-orbit coupling, while omitting diamagnetic and hyperfine structure corrections.

Define the angular momentum ladder operators by $L_{\pm }=L_x\pm i{L}_y$ and similarly for $S_{\pm }$. Direct expansion givesso adding $L_z{S}_z$ gives the required scalar product. The off-diagonal terms change $m_{\ell }$ and $m_s$ in opposite directions. Consequently $J_z=L_z+S_z$ commutes with $H$, and $m_j$ remains a good quantum number at every magnetic field.

In the given product eigenbasis, the diagonal matrix elements areFor $\ell =1$ and $s=1/2$, the only off-diagonal couplings are between $(1,-1/2)$ and $(0,1/2)$, and between $(0,-1/2)$ and $(-1,1/2)$. Each relevant orbital ladder factor is $\hslash \sqrt{2}$ and each spin ladder factor is $\hslash$. Multiplying by $K/{\hslash }^2$ gives $\sqrt{2}K$. ThereforeAll other off-diagonal entries vanish either by the ladder endpoints or by conservation of $m_j$. This derives every entry of the displayed matrix.

The stretched states have no mixing and yieldThe $m_j=1/2$ block is $\left(\begin{array}{cc}-K& \sqrt{2}K\\ \sqrt{2}K& a\end{array}\right)$, while the $m_j=-1/2$ block is $\left(\begin{array}{cc}-a& \sqrt{2}K\\ \sqrt{2}K& -K\end{array}\right)$. Taking the trace and determinant of each $2\times 2$ block gives the remaining four energy eigenvalues:The subscripts indicate $m_j=\pm 1/2$ and the superscripts indicate the upper or lower root. These formulas are the Zeeman spectrum for orbital angular momentum one and remain valid for either sign of $K$.

For the usual ordering $K>0$, including sodium, the zero-field states follow fromThe $j=3/2$ quartet lies at $K$ and the $j=1/2$ doublet at $-2K$, separated by $3K$. In a weak magnetic field, the Landé g-factors giveThese label the curves near $B=0$. In a strong magnetic field, the Paschen-Back effect makes $(m_{\ell },m_s)$ the appropriate approximate labels:for the mixed states, with the stretched-state formulas already exact. The branch connections for $B>0$ areWithin a fixed $m_j$, the nonzero coupling prevents a crossing; this is an avoided crossing. Curves with different $m_j$ may cross because the Hamiltonian does not couple them.

For the sodium estimate, the zero-field frequency separation fixesThe lower $3s$ doublet has shifts $\pm a$. The Sodium D-line Zeeman pattern gives photon-frequency shifts $a/h$ times $\{\pm 2/3,\pm 4/3\}$ for D${}_1$ and $\{\pm 1/3,\pm 1,\pm 5/3\}$ for D${}_2$. Thus the highest-frequency D${}_1$ component and lowest-frequency D${}_2$ component approach each other by $3a/h$. Extrapolating the weak-field Zeeman splitting givesso the crossover occurs at a field of order $10\mathrm{T}$, where $a\sim K$ and the weak-field approximation is becoming marginal.

The exact eigenvalues refine the estimate within this Hamiltonian. The relevant photon energies, with a common zero-field reference omitted, are $E_{+}^{(-)}+a$ and $E_{-}^{(+)}-a$. The corresponding electric dipole transitions have $\Delta m_j=+1$ and $-1$, respectively. Equating them givesIts positive solution is $a/K=\sqrt{10}/3$, hencein the retained model. The crossing is between optical transition frequencies; the participating upper states themselves need not be degenerate.

Neglect hyperfine structure and use the electronic weak-field Zeeman splitting regime, where ${\mu }_{B}B$ is small compared with the spin-orbit interaction splitting. The sodium levels are $3s{}^2{S}_{1/2}$, $3p{}^2{P}_{1/2}$ and $3p{}^2{P}_{3/2}$. The Landé g-factor formula givesFor example, inserting $L=1,S=1/2,J=1/2$ gives $3/2+(3/4-2)/(2\cdot 3/4)=2/3$. Each sublevel with magnetic quantum number $m_J$ shifts by $g_J{m}_J{\mu }_{B}B$. Thus the lower level has shifts $\pm {\mu }_{B}B$, the upper $J=1/2$ level has shifts $\pm {\mu }_{B}B/3$, and the upper $J=3/2$ level has shifts $\pm 2{\mu }_{B}B$ and $\pm 2{\mu }_{B}B/3$.

The electric-dipole selection rule allows $\Delta J=0,\pm 1$ except $0\leftrightarrow 0$, and $m_u-m_l=0,\pm 1$. Both fine structure branches are allowed. The emitted photon energy isAll the allowed components of the sodium D-line Zeeman pattern are listed below; the last column is the photon shift in units of ${\mu }_{B}B$:These are four components of D1 and six of D2. Their strengths need not be equal; the table and arrows specify allowed transitions, not intensities.

The $3p{}^2{P}_{3/2}$ level lies above $3p{}^2{P}_{1/2}$, so D2 has the larger zero-field photon energy. ^[ref] In the stated weak-field regime its most positive shift is $5{\mu }_{B}B/3$. Since $\lambda =hc/E_{\gamma }$, the shortest wavelength is therefore produced byThe tempting $m_u=3/2\to m_l=-1/2$ pair has a larger difference of level shifts but is forbidden because $|m_u-m_l|=2$.

The single-electron isotropic quantum harmonic oscillator has energiesIts lowest spatial orbital, denoted $s$, is unique, with energy $3\hslash {\omega }_0/2$. Including spin one-half gives two spin orbitals. Two identical electrons can occupy both only with opposite spin in the unique singlet state. Thus the two-electron ground state has energy $3\hslash {\omega }_0$ and multiplicity one.

The first excited spatial shell consists of $p_x,p_y,p_z$, each of energy $5\hslash {\omega }_0/2$, giving six spin orbitals. A first-excited two-electron Slater determinant occupies one of the two ground-shell spin orbitals and one of these six excited-shell spin orbitals. HenceNo further factor of two is inserted for interchanging the electrons, since the fermionic exchange symmetry is already built into a Slater determinant.

The spatial Hamiltonian operator is invariant under simultaneous rotations of both positions, so $[H_0,L_k]=0$ for each component of the total orbital angular momentum. It is also spin independent, so $[H_0,S_k]=0$ for each total spin component. Thereforeexpressing conservation of angular momentum and conservation of the total spin magnitude for this model. The Pauli exclusion principle restricts which states occur but does not break either symmetry.

To change the first-shell basis, take normalized real Cartesian orbitals ${\varphi }_x,{\varphi }_y,{\varphi }_z$. Using spherical coordinates, $z=r\cos \theta$ and $x\pm iy=r\sin \theta e^{\pm i\phi }$. Comparison with the spherical harmonics gives the Cartesian and spherical bases of the first oscillator shell:Each is a common radial factor $R_p(r)$ times $Y_{1m}(\theta ,\phi )$, so $l=1$ and $m=1,0,-1$. Their normalizations and mutual orthogonality follow because this is a unitary change of basis. The ground spatial orbital has $l=0$.

For two ground-shell electrons, addition of angular momentum gives $L=0$, and their symmetric spatial state requires $S=0$. For one electron in each shell, $0\otimes 1$ gives only $L=1$. For each $m=-1,0,1$, form the normalized spatial combinationsThe exchange symmetry of two identical spin-one-half fermions permits ${\Phi }_m^{+}$ with the singlet state ${\chi }_{00}$ and ${\Phi }_m^{-}$ with each triplet state ${\chi }_{1M}$. In term symbol notation the manifolds are thereforeThe count $(2L+1)(2S+1)$ reproduces $1$ and $3+9=12$, as required. Both exchange symmetries are possible for the distinct occupied orbitals; dropping either spin sector would undercount the two-electron states in the first two shells of an isotropic oscillator.

For the specified spin-orbit interaction, $\mathbf{S}$ and $\mathbf{L}$ are the total two-electron operators. Set $\mathbf{J}=\mathbf{L}+\mathbf{S}$. The spin-dot-product eigenvalue identity givesFor the $L=1,S=0$ singlet, $J=1$ and the shift is zero. For the $L=S=1$ triplet, $J=0,1,2$. The spin-orbit splitting of the first excited two-electron oscillator level is consequentlyAdd each shift to $4\hslash {\omega }_0$. The multiplicities sum to twelve and their weighted shift sums to zero. For positive $\lambda$ the table is ordered in energy; for negative $\lambda$ the ordering reverses. Weak coupling means $|\lambda |{\hslash }^2\ll \hslash {\omega }_0$. Since this total-spin interaction commutes with $H_0$, $L^2$ and $S^2$, the shifts within this invariant manifold are in fact exact for the specified model, although only first order was requested.

Use the uncoupled angular momentum eigenstates $|m_L,\uparrow ⟩$ and $|m_L,\downarrow ⟩$, with $m_L=-1,0,1$. For the Hamiltonian operator actually written in the paper, these are the energy eigenstates, withThe initial $J=3/2$ states are not all energy eigenstates of this operator. To find their energy populations, first perform the Clebsch-Gordan decomposition. The extremal states are $|3/2,3/2⟩=|1,\uparrow ⟩$ and $|3/2,-3/2⟩=|-1,\downarrow ⟩$. Applying the total angular momentum lowering operator to the first givesSimilarly,The initial preparation is an equal incoherent mixture of the four coupled states. Each extremal state contributes population $1/4$ to its one energy eigenvalue, while each nonextremal state contributes $2/3$ and $1/3$ of its own $1/4$ population to the two displayed components. The resulting Zeeman splitting is thereforefor nonzero $B_z$. The relative populations are $\boxed{3:2:2:2:3}$ in this order; the two zero-energy states each have population $1/12$. These Zeeman populations from an unpolarized angular-momentum multiplet remain constant under subsequent evolution by the stated static Hamiltonian operator, although off-diagonal quantum coherence can evolve.

There is a distinct weak-field model in which a retained spin-orbit interaction keeps $J=3/2$ isolated and one projects the magnetic perturbation into that quartet. The Landé g-factor is then $4/3$, giving four shifts ${\mu }_B{B}_z(\pm 2,\pm 2/3)$ with equal populations. That calculation requires the additional projection or dominant spin-orbit interaction; it is not diagonalization of the full magnetic Hamiltonian operator specified here, which also mixes the $J=1/2$ sector.

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.

A nonrelativistic $2p$ wavefunction vanishes linearly at the origin. Its probability density is therefore proportional to $r^2$, so its first-order finite nuclear size correction shift scales as $R^4$, rather than the $R^2$ result for $1s$. It is positive but much smaller.

More explicitly, the normalized hydrogen-like ion radial function obeys $R_{21}^2(r)\simeq Z^5{r}^2/(24a_0^5)$ near the origin. Since the spherical harmonic has unit angular norm,ThusThis is about $2.4\mu \mathrm{eV}$ in the nonrelativistic model. At large $Z$, the relativistic $2p_{1/2}$ Dirac spinor has an $s$-type small component and a much stronger nuclear sensitivity than this nonrelativistic argument predicts; $2p_{3/2}$ remains much more suppressed. Neglecting spin-orbit interaction corrections would miss that distinction.

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.

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.

Take the field along $z$ and write $x={\mu }_{B}B$, with Bohr magneton ${\mu }_B$. The printed Hamiltonian uses dimensionless angular-momentum operators, with eigenvalues $L(L+1)$ and $m_L$; physical angular momenta carry an additional $\hslash$. Thus $\beta$ and $x$ are energies. Assume the usual positive spin-orbit interaction coefficient $\beta >0$. Reversing its sign reverses the zero-field ordering but not the state count.

An electron has $S=1/2$. addition of angular momentum givesThe coupled angular-momentum state count can be checked directly. The product basis contains $(2L+1)\times 2=4L+2$ states. The coupled basis containsCoupling therefore reorganizes the states rather than creating or losing them. There is no hyperfine multiplicity because $I=0$.

Use $\mathbf{J}=\mathbf{L}+\mathbf{S}$ to obtainThe two spin-orbit interaction energies are $\beta L/2$ and $-\beta (L+1)/2$. In a weak field, project the Zeeman effect onto a fixed $J$ multiplet:This is the first-order energy formula, not a statement that $H_Z$ has no matrix elements between different $J$ values. For a common $m=m_J$ and a conventional choice of relative phase, its complete coupled-basis block isThe inter-multiplet Zeeman coupling terms give second-order weak-field corrections because the two spin-orbit interaction multiplets are already separated.

In the strong-field basis the Zeeman part is diagonal, $E_Z=x(m_L+2m_S)$. WriteIts diagonal matrix elements are $\beta m_L{m}_S$. Its off-diagonal matrix elements connect $(m_L,+1/2)$ to $(m_L+1,-1/2)$ with coefficientand the reverse spin change has $m_L+1$ replaced by $m_L-1$ in the corresponding ladder coefficient. These terms preserve $m_J$ but mix the two product states. To first order in $\beta /x$, the energy correction is simply $\beta m_L{m}_S$.

For the P state, $L=1$. Measured relative to its gross-structure centroid, the six low-field levels areThus the upper quartet starts at $\beta /2$ with slopes $+2,+2/3,-2/3,-2$ in a plot against $x$; the lower doublet starts at $-\beta$ with slopes $\pm 1/3$. Their zero-field separation is $3\beta /2$.

At high field all six product-state energies, retaining the term linear in $\beta$, areThe two zero-slope levels have different $m_J$ and no mutual matrix element, so their first-order degeneracy does not require an additional degenerate perturbation. At finite field they split at order ${\beta }^2/x$.

An exact interpolation makes the requested whole-field sketch unambiguous. The stretched levels areFor $m=\pm 1/2$, use product states $|m-1/2,+1/2⟩$ and $|m+1/2,-1/2⟩$. Their Hamiltonian block issoThese energies reduce to the quartet and doublet at zero field and to the six strong-field expressions above. Within a fixed $m_J$, the nonzero off-diagonal element prevents a crossing of the two branches. Levels in different $m_J$ sectors can cross without hybridizing. For the S state, $L=0$ and the spin-orbit interaction term vanishes, leavingthroughout this Hamiltonian's range of validity.

For electric dipole transitions at low field, $\Delta J=0,\pm 1$ and $\Delta m_J=0,\pm 1$ apply, with the usual exclusion of $J=0\to 0$. Each P state has opposite parity to the S state. The $P_{1/2}\to S_{1/2}$ transition has four allowed sublevel pairs. For $P_{3/2}\to S_{1/2}$, the two stretched upper states each have one destination and the other two each have two, giving six. Hence there are 10 allowed state-to-state channels at weak nonzero field. Relative to the two zero-field transition energies, their Zeeman shifts are

In the decoupled high-field limit, an electric dipole acts on orbital coordinates, so $\Delta m_S=0$. Each of the six P product states connects to the S state with the same spin and $m_L^{\prime }=0$. Thus there are 6 allowed channels in the limiting product-state description. Their photon energies areThis Paschen-Back transition-channel count is not the count of distinct frequencies: to first order in $\beta$ the two $m_L=0$ channels coincide, giving 5 distinct frequencies, with shifts $0,\pm (x+\beta /2),\pm (x-\beta /2)$. If the residual spin-orbit interaction splitting is unresolved there are the three usual orbital Zeeman groups.

The apparent loss of four channels is a change in eigenstate mixing, not a change in Hilbert-space dimension. At finite large field, four weak spin-forbidden Paschen-Back lines arise from small opposite-spin admixtures, with intensities vanishing as $(\beta /x{)}^2$. A generic finite-field calculation therefore retains ten nonzero channels; six carry finite strength in the complete-decoupling limit. Observation direction and polarization select which of these channels a detector actually receives.

Operators, quantization and rotations. Angular momentum is the generator of spatial rotations. In quantum mechanics, its components are Hermitian operators on their appropriate domains and obeyThese angular momentum commutation relations prevent all three components from having simultaneous sharp values. For example, the Robertson uncertainty principle gives $\Delta J_x\Delta J_y\ge \hslash |⟨J_z⟩|/2$. One conventionally diagonalizes ${\hat{J}}^2$ and a selected component ${\hat{J}}_z$:The allowed labels are $j=0,\frac{1}{2},1,\frac{3}{2},\dots$ and $m=-j,-j+1,\dots ,j$. An angular-momentum multiplet has $2j+1$ states. The magnitude $\hslash \sqrt{j(j+1)}$ differs from the largest possible component $\hslash j$; the remaining components fluctuate even in a state with maximal $m$.

The angular momentum lowering operator and its raising counterpart, ${\hat{J}}_{\pm }={\hat{J}}_x\pm i{\hat{J}}_y$, satisfyThe ladder terminates at $m=\pm j$. A rotation through angle $\theta$ about unit vector $\hat{\mathbf{n}}$ acts through the unitary operator $\exp [-i\theta \hat{\mathbf{n}}\cdot \hat{\mathbf{J}}/\hslash ]$. Thus quantized components and the continuous rotation of a state are compatible.