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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]

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.

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.

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.

Orbital angular momentum. The orbital contribution is associated with motion in space:For a spinless spatial wavefunction, the simultaneous angular eigenfunctions are the spherical harmonics $Y_{\ell m}(\theta ,\varphi )$, with $\ell =0,1,2,\dots$ and $m=-\ell ,\dots ,\ell$. Single-valued ordinary scalar spatial wavefunctions give integer orbital labels. In a central potential energy, $[\hat{H},{\hat{L}}^2]=[\hat{H},{\hat{L}}_z]=0$, so stationary states may be labelled by these angular quantum numbers. The angular kinetic contribution appears in the radial equation as $\ell (\ell +1){\hslash }^2/(2m{r}^2)$, the centrifugal potential. Noncentral interactions need not conserve these orbital labels.

Intrinsic spin and addition. Spin angular momentum is an intrinsic internal degree of freedom with the same commutation algebra. It is not the angular momentum of a small classical charged sphere literally rotating about its centre. For an Electron, $s=1/2$ and $m_s=\pm 1/2$, so ${\hat{S}}_i=(\hslash /2){\sigma }_i$ in terms of the Pauli matrices. Its squared spin is $3{\hslash }^2/4$. Other particles can have integer or half-integer spin, including spin zero.

For one particle with orbital and spin degrees of freedom, $\hat{\mathbf{J}}=\hat{\mathbf{L}}+\hat{\mathbf{S}}$; the two component sets commute with each other. Addition of angular momentum permits $j=|\ell -s|,|\ell -s|+1,\dots ,\ell +s$. The coupled states $|j,m_j⟩$ are linear combinations of the uncoupled $|\ell ,m_{\ell }⟩|s,m_s⟩$ with $m_j=m_{\ell }+m_s$, determined by Clebsch-Gordan coefficients. A rotationally invariant spin-orbit interaction can conserve $J^2,J_z$ while mixing the separate component labels.

Angular momentum also carries a magnetic moment. For an electron's orbital motion and intrinsic spin,The minus signs reflect negative electric charge. With the Bohr magneton ${\mu }_B=e\hslash /(2m_e)$, a spin projection $m_s$ has ${\mu }_z=-g_s{\mu }_B{m}_s$. A magnetic field can therefore distinguish angular-momentum states through their interaction energy $-\mathbf{\mu }\cdot \mathbf{B}$.

Stern–Gerlach measurement. In the Stern-Gerlach experiment, atoms emerge from a heated source, pass through collimating apertures, traverse a strongly inhomogeneous magnetic field, and strike a position-sensitive screen. The beam is neutral, so its separation is interpreted through the atomic magnetic moment rather than the ordinary charged-particle Lorentz force. Near a chosen quantization direction, the interaction givesA uniform field can exert a torque but would not separate the beam by this translational force; the gradient is essential. Different allowed magnetic-moment components become correlated with different trajectories. A classical ensemble with continuously varying orientations would yield a continuous spread, whereas discrete quantum components yield separated channels.

In the modern electronic description of ground-state silver, filled shells cancel their electronic angular momenta and the unpaired $5s$ electron has $L=0$, $S=1/2$, $J=1/2$. The effective electronic measurement therefore has two components, approximately ${\mu }_z=\pm {\mu }_B$, rather than an orbital $\ell =1/2$, which is not allowed. For positive field gradient the electronic $m_J=+1/2$ component has negative ${\mu }_z$ and deflects downward in this coordinate convention. Nuclear spin and hyperfine structure are neglected in this simplified two-channel account. Historically the original splitting preceded the electron-spin interpretation, so the modern explanation should not be confused with the original investigators' interpretation.

More generally a prepared spin state $a|+z⟩+b|-z⟩$ gives the two outcomes with probabilities $|a{|}^2,|b{|}^2$. Selecting one channel prepares a state for further measurements. An ideal second analyser along the same axis then gives a definite result, whereas one along a perpendicular axis gives two equally likely outcomes for a spin-one-half eigenstate. This connects the apparatus directly to incompatible spin components and the Born rule. Angular momentum is quantized through its operator algebra; the Stern–Gerlach gradient turns that discrete internal information into spatially distinguishable outcomes.

The total angular momentum operator is $\mathbf{J}=\mathbf{L}+\mathbf{S}$. Since orbital and spin operators act on different factors of the tensor product, they commute, and expanding $J^2$ givesA coupled angular momentum eigenstate $|l,s;j,m_j⟩$ is a simultaneous eigenstate of these three squared operators, with eigenvalues ${\hslash }^{2}j(j+1)$, ${\hslash }^{2}l(l+1)$ and ${\hslash }^{2}s(s+1)$. Thus the angular factor in the spin-orbit interaction is the numberThe other factor, $r^{-1}dV/dr$, is radial. It commutes with the angular operators, and a central-potential energy eigenstate separates into a radial wavefunction and an angular spinor. Taking its radial expectation value therefore givesThis spin-orbit energy shift in a central potential is independent of $m_j$, so rotational symmetry preserves the $2j+1$ magnetic degeneracy within a fixed $j$ multiplet. It is a first-order fine structure correction; the given coefficient already includes the relativistic factor needed for the electron's spin-orbit coupling.

The attractive Coulomb potential energy is $V(r)=-e^2/(4\pi {ϵ}_{0}r)$, soUse precisely the radial normalization stated in the PDF: the radial probability measure is $4\pi r^2|\psi {|}^{2}dr$. The supplied function hasIts integral is one, since ${\int }_0^{\infty }{r}^4{e}^{-r/a_0}dr=24a_0^5$. In particular,This calculation uses the supplied convention, rather than multiplying a separately normalized standard radial function by an extra $4\pi$.

The addition of angular momentum bracket is $j(j+1)-l(l+1)-s(s+1)=3/4-2-3/4=-2$. Substitution in the spin-orbit energy shift in a central potential therefore givesHere $a_0=5.29\times 10^{-11}\mathrm{m}$ is the supplied Bohr radius. The negative sign means the $j=1/2$ member of the $l=1$ pair is shifted downward by this spin-orbit interaction; it is not the total hydrogen binding energy.

For the isotropic three-dimensional quantum harmonic oscillator, $V(r)=m{\omega }^2{r}^2/2$, hence $r^{-1}dV/dr=m{\omega }^2$ is constant. No radial integral remains, so the spin-orbit energy shift in a central potential reduces toFor $l=0$, the only possibility is $j=1/2$, and the bracket vanishes. For $l=1$, coupling to spin one-half permits $j=1/2$ and $j=3/2$, whose brackets are $-2$ and $+1$. ThusThese spin-orbit shifts of an isotropic harmonic oscillator are a zero line, a downward parabola, and an upward parabola of half the downward magnitude. They are independent of the radial excitation number, and their magnetic multiplicities are respectively two, two and four. Their weighted mean within the $l=1$ manifold is zero: $2\Delta E_{1,1/2}+4\Delta E_{1,3/2}=0$.

The Rashba effect, named for Emmanuel Rashba, is a momentum-dependent spin-orbit interaction associated with broken spatial inversion symmetry. In an isotropic two-dimensional model, choose $\lambda >0$ and write the Hamiltonian $H={\hslash }^2{k}^{2}I/(2m)+\lambda (\hat{\mathbf{z}}\times \mathbf{k})\cdot \mathbf{\sigma }$, where $I$ is the identity matrix and $\mathbf{\sigma }$ is the vector of Pauli matrices. The eigenvalues of the spin term give $E_{\pm }(k)={\hslash }^2{k}^2/(2m)\pm \lambda k$. Define $k_R=m\lambda /{\hslash }^2$ and $E_R={\hslash }^2{k}_R^2/(2m)$. The lower branch is $E_{-}(k)={\hslash }^2(k-k_R{)}^2/(2m)-E_R$ and has a ring of minima at $k=k_R$. A negative $\lambda$ reverses the spin directions; ordering the two energies still uses $|\lambda |$. The alternative parameter $q_R=2k_R$ must not be mistaken for the minimum radius.

Neglect hyperfine structure and use a magnetic field weak compared with the spin-orbit interaction. The sodium D doublet has transitions $3p{}^2{P}_{1/2}\to 3s{}^2{S}_{1/2}$ and $3p{}^2{P}_{3/2}\to 3s{}^2{S}_{1/2}$. Their Landé g-factors are $2/3$, $4/3$ and $2$ respectively. With $m_u,m_l$ denoting upper and lower magnetic labels, the photon shift isThe first transition has four allowed shifts ${\mu }_{B}B\{\pm 2/3,\pm 4/3\}$; the second has six, ${\mu }_{B}B\{\pm 1/3,\pm 1,\pm 5/3\}$. The most blue-shifted component of the second is $m_u=1/2\to m_l=-1/2$, with shift $5{\mu }_{B}B/3$. The apparently larger shift $m_u=3/2\to m_l=-1/2$ is excluded by the electric-dipole selection rule. The $3p{}^2{P}_{3/2}$ level lies above $3p{}^2{P}_{1/2}$, so in this weak-field model the $5/3$ component also has the shortest wavelength of the whole doublet. ^[ref]

For a central-potential Hamiltonian operator with the spin-orbit interaction $H_{\mathrm{so}}=[r^{-1}{V}^{\prime }(r)/(2m^2{c}^2)]\mathbf{L}\cdot \mathbf{S}$, use $\mathbf{J}=\mathbf{L}+\mathbf{S}$ andA coupled angular momentum eigenstate makes this angular factor a number. The radial operator commutes with all angular factors, giving the energy shift in the title. It is independent of the magnetic projection $m_j$, so a fixed-$j$ multiplet retains its $2j+1$ degeneracy.

For spin one-half, the angular bracket is $l$ when $j=l+1/2$ and $-(l+1)$ when $j=l-1/2$. Only the former exists at $l=0$, where it is zero. For the Coulomb potential energy, $r^{-1}{V}^{\prime }(r)=e^2/(4\pi {ϵ}_0{r}^3)$; the radial normalization convention must be respected when computing its expectation value.

An equal incoherent mixture within a fixed total-$J$ multiplet has density operator $\rho =P_J/(2J+1)$, where $P_J$ is its orthogonal projection. If the applied-field Hamiltonian operator is proportional to $L_z+2S_z$ and no spin-orbit interaction is retained, its energy eigenstates are the uncoupled states $|m_L,m_S⟩$. The Born rule gives their populations by the formula above, or equivalently by squared Clebsch-Gordan decomposition coefficients. Equal populations of coupled states need not give equal populations of magnetic energy eigenvalues.

For $L=1,S=1/2,J=3/2$, the nonextremal coupled states have weights $2/3$ and $1/3$ in their two uncoupled components. The five dimensionless magnetic energies $-2,-1,0,1,2$ then have populations $1/4,1/6,1/6,1/6,1/4$; the zero energy contains two independent states, each with population $1/12$. In a different, weak-field approximation with a dominant spin-orbit interaction, projecting into the isolated multiplet gives the Landé g-factor spectrum instead. The full operator and its projection must not be interchanged.