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In 1947, Willis Eugene Lamb Jr. and Robert Curtis Retherford dissociated hydrogen in a tungsten oven, crossed its atomic jet with electrons for collisional excitation, and detected surviving $2S$ atoms by electron ejection from metal. An electrometer and galvanometer read the current. They interrupted fixed-frequency microwaves while sweeping the static magnetic field; a flip coil calibrated the field. Their Zeeman splitting comparison placed $2S_{1/2}$ about $1000$ $\mathrm{MHz}$ above $2P_{1/2}$; the plotted $1000$ $\mathrm{MHz}$ displacement was explicitly not a best fit.^[ref]

The 1955 lecture's apparatus cross-section identifies movable slits, an electron bombarder, a radiofrequency transmission line with beam slots, a d.c. quenching electrode, metal target, electron collector, and magnet poles. A $2S\to 2P$ transition followed by rapid spontaneous emission leaves a ground-state atom unable to eject detector electrons. The scan holds radiofrequency and amplitude fixed. Natural linewidth and unresolved hyperfine structure broaden resonances, whose analysis yields zero-field separations.^[ref]

Static electric field quenching supplied a control. The 1947 report identifies natural linewidth, hyperfine structure, excessive microwave intensity, and field inhomogeneity as width contributions, and flags imperfect magnetic calibration. It does not specify an absolute microwave-frequency calibration procedure.^[ref]

The surname is Robert Curtis Retherford's: “Retherford” and “Rutherford” name different people. The historical Lamb-Retherford experiment should retain the former spelling.^[ref]

Consider an original illustrative resonance model, with all numerical settings chosen here. On one isolated branch approximate the transition frequency by $\nu (B)={\nu }_0+aB$, with known slope $a=20MHz/mT$ and drive frequency ${\nu }_d=1300\mathrm{MHz}$. Choose ${\nu }_0=1100\mathrm{MHz}$, hence resonance field $B_r=10\mathrm{mT}$. This local linear model omits hyperfine structure and nonlinear level mixing; it is not the historical hydrogen Zeeman splitting calculation.

Use a Lorentzian line shape for a weak-drive current dip,Choose baseline $C=1$, depth $A=0.25$ in arbitrary detector signal units, and full width at half maximum $w_{\nu }=100\mathrm{MHz}$, so $w_B=5\mathrm{mT}$. The half-depth points are $B_r\pm w_B/2$; this checks the factor of four. If an exponential decay with lifetime $\tau$ alone set this width, natural linewidth would give $w_{\nu }=1/(2\pi \tau )$ and $\tau \simeq 1.59\mathrm{ns}$. The chosen width is an explanatory input, not a measurement of a historical lifetime.

Generate 65 equally spaced fields from $2$ to $18\mathrm{mT}$ and add independent Gaussian noise with known standard deviation ${\sigma }_I=0.004$ signal units. A simultaneous nonlinear regression fit of $C,A,B_r,w_B$ gives $B_r\simeq 10.0007\mathrm{mT}$, $w_B\simeq 4.9305\mathrm{mT}$ and ${\nu }_0\simeq 1099.986\mathrm{MHz}$. With residual derivatives $J_{ik}=\partial I(B_i)/\partial {\theta }_k$ and $\theta =(C,A,B_r,w_B)$, the local covariance matrix estimate isIt gives centre standard deviation $0.01427\mathrm{mT}$, or $0.285\mathrm{MHz}$ in the inferred intercept. This uses the stipulated noise variance and a local linear approximation, rather than treating the width as the centre error. Repeated noisy samples can locate a broad line's centre much more closely than its width.

Include a common magnetic calibration offset with standard deviation $u_b=0.020\mathrm{mT}$, a fractional gain error $u_g=0.001$, and independent drive-frequency error $u_d=0.100\mathrm{MHz}$. To first order the inferred variance isHere $u$ denotes a standard uncertainty, not a frequency. The four contributions in $\mathrm{MHz}$ are $0.285$, $0.400$, $0.200$, and $0.100$; adding their squares gives $u({\nu }_0)\simeq 0.540\mathrm{MHz}$. The calibration offset shifts all sampled fields together, so increasing the sample count cannot average it away. Uncertainty in $a$, unresolved components, asymmetric line distortion, and errors in the assumed field dependence would require additional terms or a richer model. The historical inference requires the appropriate Zeeman splitting branches, rather than simply drawing a straight line through one resonance.

For dimensionless angular momentum operators and a Hamiltonian $H=a\mathbf{I}\cdot \mathbf{J}$ at fixed $I,J$, addition of angular momentum gives $E_F=a[F(F+1)-I(I+1)-J(J+1)]/2$. Subtracting neighbouring energy levels proves the displayed rule. For fine structure substitute $\mathbf{L},\mathbf{S}$ and total $J$; for magnetic-dipole hyperfine structure use electronic $J$, nuclear spin $I$ and total $F$. Electric-quadrupole interactions and mixing with nearby energy levels can violate the rule.

For weak-field sodium D lines neglecting hyperfine structure, the smallest adjacent spectral spacing in the full electronic pattern is $s_E=2{\mu }_{B}B/3$. A drawing without a labelled energy axis can still estimate $B$ if it includes both unsplit D lines with known wavelengths: their separation calibrates $hc(1/{\lambda }_2-1/{\lambda }_1)$. Divide the drawn split spacing by the drawn unsplit separation before using that energy scale. Graphical line thickness, unequal drawn spacings and uncalibrated rendering limit precision; they do not justify exact numerical field values.

Maser state selection separates paths according to the Stark effect, the dependence of a molecule's energy levels on an electric field. It prepares a transmitted population by sorting. Optical pumping, by contrast, changes populations through absorption of light and subsequent transitions. Both can produce a useful population imbalance, but they are different preparation mechanisms.

A simple two-level system explains the sign of the focusing force. Ignore additional splittings and let the magnitude of the relevant projected electric dipole moment be $d$. Model the two local energy levels in an electric field of magnitude $\mathcal{E}$ byFor an ideal quadrupolar electrostatic potential $\Phi =A(x^2-y^2)$, the electric field magnitude is $\mathcal{E}=2|A|r$, where $r=\sqrt{x^2+y^2}$. Since $W_{+}$ increases with $r$, the force ${\mathbf{F}}_{+}=-\nabla W_{+}$ points inward. The lower branch has the opposite sign and is defocused. The upper branch is thus low-field seeking. This argument uses the gradient of internal energy, rather than a net electric charge on the molecule. The square-root splitting is the usual two-state description.^[ref] The idealized two-level system omits the actual rotational and hyperfine structure sublevels and their different transmission efficiencies.

Microwave spectroscopy measures a system's response in the microwave frequency range. Molecular rotation, atomic hyperfine structure and transitions shifted by external fields can occur at these frequencies; the physical transition must be identified rather than inferred from the word microwave alone.

A frequency-scanned source can drive a sample while a detector records absorption or a changed state population. The Lamb shift experiment provides a historical atomic example: a microwave field transfers metastable hydrogen atoms to a state that decays rapidly, allowing a downstream state-sensitive signal to reveal the resonance. The measured quantity is a change in detector response versus frequency, from which a transition energy is inferred.

Recovering molecular geometry from rotational constants is an inverse problem. In the synthetic assignment, $B=5\times 10^9\mathrm{Hz}$ gives $I=h/(8{\pi }^{2}B)\simeq 1.6784\times 10^{-45}\mathrm{kg}{\mathrm{m}}^2$. For a diatomic molecule with known masses, rotational constant explains how to infer an effective bond length. For a longer linear molecule, one $I$ cannot determine every bond length: several different arrangements can have the same moment of inertia.

For a fixed three-atom linear model with positions $0,a,a+b$ and positive masses $m_1,m_2,m_3$, subtracting the centre of mass givesThis is one equation for two unknown bond lengths. Even fixing the order of the chemical atoms leaves a family of solutions. Additional isotope substitutions change known masses and supply independent equations, provided the effective molecular geometry can be treated as shared. For nonlinear molecules, three principal moments of inertia give frequency-valued constants $A=h/(8{\pi }^2{I}_a)$, $B=h/(8{\pi }^2{I}_b)$, and $C=h/(8{\pi }^2{I}_c)$; a single evenly spaced comb is generally insufficient.

Vibrational averaging, unresolved hyperfine structure, internal motion, and centrifugal distortion limit structural inference. A ground-vibrational fitted rotational constant is not automatically the equilibrium constant. Ordinary field-free rotational spectroscopy also gives identical spectra for opposite enantiomers under the usual parity-symmetric molecular Hamiltonian; assigning composition and conformation does not by itself determine handedness. Molecular identification from a rich fingerprint can therefore succeed even when a unique full molecular geometry cannot be reconstructed.

Let $v$ be the source velocity towards the absorber, positive for approach along the photon direction. A first-order Lorentz transformation of the photon energy gives $E^{\prime }=E+vp$; hence, for $|v|\ll c$,Moving the source shifts its emission line through the stationary absorption line. A minimum in transmitted photon counts marks their strongest overlap. The absorber is the narrow energy discriminator; the downstream particle detector only needs to count the transmitted gamma rays.

For a thin absorber with unsplit Lorentzian line shapes, the overlap is a convolution of the source and absorber profiles. The combined full width at half maximum is $W={\Gamma }_s+{\Gamma }_a$. A simple expected transmission model isHere $I_0$ is the off-resonance intensity, $v_0$ encodes a relative shift of the two transition energies, and $A$ includes the resonant absorber strength and $f_s{f}_a$. The convolution result can be checked by multiplying the Fourier transforms of two Cauchy distributions: their exponential decay constants add. The width of the absorption dip in velocity is $cW/E_{\gamma }$, rather than the width of one individual spectral line converted to velocity.

For the teaching system with ${\Gamma }_s={\Gamma }_a={\Gamma }_E$ and $v_0=0$, the dip's full width at half maximum is $2.9979\mathrm{mm}{\mathrm{s}}^{-1}$. Stipulate $A=0.25$ at zero temperature and $10,000$ expected off-resonance counts per equal-duration bin: the central bin then has $7,500$ expected counts, and the half-depth bins have $8,750$. These are model expectations, without sampled counting noise. Holding all other parameters fixed while heating both lattices to $k_{B}T=2\hslash \omega$ multiplies $A$ by $[f(T)/f(0){]}^2$. This isolates how a falling recoil-free fraction weakens the dip.

The thin-absorber model is deliberately limited. A thick absorber can saturate and broaden the dip; unresolved hyperfine structure can create multiple components. Differences in chemical surroundings can shift the centers, and uncontrolled motion can smear them. These effects must be modeled before interpreting an observed width as a natural linewidth. Their sensitivity also makes the Mössbauer effect useful: a small displacement of a narrow dip can reveal a small change in the local nuclear environment.

The normal Zeeman effect is the simple three-frequency pattern obtained in the orbital limit. Assume negligible net spin, negligible hyperfine structure and quadratic shifts, and an allowed electric-dipole interaction between levels with orbital splitting factor one. A level with $J=0$ has only $m_J=0$ and no first-order shift. For the other levels, $g_J=1$ gives $\Delta E={\mu }_B{m}_{J}B$. Define $q=m_u-m_l$, rather than the final-minus-initial change of the emitting atom. The electric-dipole selection rule allows $q=0,\pm 1$, henceMany allowed transitions can share one frequency; a triplet need not mean exactly three transitions. The cleanest illustrative example is $J_u=1\to J_l=0$, with three upper quantum states and one unshifted lower quantum state. The $q=0$ component is called $\pi$, and $q=\pm 1$ components ${\sigma }^{\pm }$ with this stated convention. During emission the atom changes its magnetic quantum number by $-q$.

For an original numerical example choose $B=0.50\mathrm{T}$ and a zero-field vacuum wavelength ${\lambda }_0=500\mathrm{nm}$. Using ${\mu }_B\simeq 9.27401\times 10^{-24}\mathrm{J}{\mathrm{T}}^{-1}$ and $h=6.62607015\times 10^{-34}\mathrm{J}\mathrm{s}$ gives $\delta {\nu }_B\simeq 7.00\mathrm{GHz}$. The two outer components are separated by $2\delta {\nu }_B\simeq 14.0\mathrm{GHz}$. Differentiating the vacuum relation $\lambda =c/\nu$, with $c$ the speed of light, givesEach outer component lies about $0.00584\mathrm{nm}$ from the centre. Positive $q$ means higher frequency and shorter wavelength. Equal spacing in frequency is only approximately equal spacing in wavelength. These are calculated values for a chosen model, not historical measurements.

The magnetic dipole moment associated with nuclear spin, using dimensionless angular momentum operators and the nuclear magneton ${\mu }_N$. The quoted scalar moment is its expectation in the stretched quantum state, ${\mu }_I=g_I{\mu }_{N}I$. In the same electronic energy level, the leading magnetic-dipole hyperfine structure constant is proportional to ${\mu }_I/I$, apart from isotope-dependent electronic and nuclear-size corrections.

The electric quadrupole moment of an atomic nucleus, conventionally specified in its stretched nuclear spin state. It measures a nonspherical nuclear charge distribution. Its interaction with the electronic electric-field gradient contributes to hyperfine structure and generally changes the magnetic-dipole Landé interval rule. A permanent rank-two moment vanishes for nuclear spin less than one.

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 open shell contains one $f$ electron, so $L=3$ and $S=1/2$. For a less-than-half-filled shell, Hund's rules select the smaller total angular momentum, $J=L-S=5/2$, giving the free-ion ground level ${}^2{F}_{5/2}$. The Landé g-factor isIn a magnetic field weak compared with the spin-orbit splitting, the electronic Zeeman shifts are $\delta E_{m_J}=g_J{\mu }_{B}B{m}_J$, for $m_J=-5/2,-3/2,\dots ,5/2$. Thus six equally spaced magnetic substates appear. At $B=1\mathrm{T}$, the adjacent-level spacing isThe complete lowest-to-highest multiplet spread is five spacings,Giving both quantities removes the ambiguity in the word splitting. This is the free-ion, weak-field result; no crystal-field doublet or hyperfine structure is specified.

Use the isolated nuclear spin Zeeman effect implied by the supplied nuclear magnetic moment, with hyperfine structure neglected. The proton gyromagnetic ratio isThe two spin levels are separated by $g_p{\mu }_N{B}_0$. Resonant nuclear magnetic resonance therefore requires the Larmor frequency

The duration is a Rabi pi pulse: in a frame rotating with the resonant transverse magnetic field, the spin must rotate through $\pi$. If $B_1$ denotes the magnitude of a circularly rotating field with the correct sense of rotation, the Rabi angular frequency is ${\Omega }_R={\gamma }_p{B}_1$. The shortest pulse is then

There is an amplitude convention to specify. If the applied transverse magnetic field is instead the linearly oscillating $B_1\cos (\omega t)\hat{\mathbf{x}}$, its resonant circular component has magnitude $B_1/2$. The rotating-wave approximation gives ${\Omega }_R={\gamma }_p{B}_1/2$ and henceThe wording does not specify this polarization convention, so the two pulse durations should be distinguished. Odd multiples of either shortest Rabi pi pulse also invert the spin within the corresponding ideal 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 $|m_u-m_l|=2$.

Use the electronic weak-field Zeeman splitting model, neglecting hyperfine structure. The Landé g-factor is $g_g=2$ for $3S_{1/2}$ and $g_e=2/3$ for $3P_{1/2}$. The shift of an absorption frequency is thereforeHere the magnetic field is weak relative to spin-orbit coupling, so $J$ remains a useful quantum number, but the spectral line widths are small enough to resolve its magnetic substates.

For linear polarization parallel to $z$, the optical electric field has only the field-axis $\pi$ component. The electric-dipole selection rule is $\Delta m=0$. Its two allowed transitions are $m_g=m_e=\pm 1/2$, givingFor propagation perpendicular to $z$ with linear polarization also perpendicular to $z$, the optical electric field is an equal-amplitude combination of the two field-axis circular components. It drives ${\sigma }^{\pm }$ transitions with $\Delta m=\pm 1$. These connect $-1/2\to +1/2$ and $+1/2\to -1/2$, givingThus each orientation selects two lines, with twice the separation in the perpendicular-polarization case. Neither pair has an unshifted central component. This is polarization-selective Zeeman splitting of an alkali D1 line, an anomalous Zeeman effect rather than a normal orbital triplet.

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.

Neglect hyperfine structure, spin-orbit coupling and the diamagnetic term, and set $b={\mu }_{B}B$, $\epsilon =\alpha a_0^2$. The Zeeman energy is $b(L_{\hat{B}}+2S_{\hat{B}})$. The electron spin is free, so every spatial result below is duplicated with an added $\pm b$.

For a magnetic field parallel to $z$, the old magnetic quantum number $m$ remains good and the first-order energy levels areThe two $s$ orbitals have zero orbital angular momentum, so only their electron spin contributes at this order.

For a magnetic field parallel to $x$, the expectation of $L_x$ in each individual $p_m$ orbital vanishes. One must still check the degenerate $m=\pm 1$ subspace: its projected $L_x$ is zero as well. Thus there is no first-order orbital splitting in a sufficiently weak transverse magnetic field. Spin still contributes $\pm b$.

The transverse orbital Zeeman mixing can be seen without assuming its size. Put $E_0=-\mathrm{Ry}/4+3\epsilon$, $E_t=-\mathrm{Ry}/4+21\epsilon$, and $\Delta =E_t-E_0=18\epsilon$. In the real $p_x,p_y,p_z$ orbital basis, $p_x$ is unaffected while $p_y,p_z$ have off-diagonal matrix elements of modulus $b$. Diagonalizing this two-dimensional Hamiltonian gives the spatial energy eigenvaluesWhen $b\ll \Delta$, their shifts relative to the earlier levels are $0,+b^2/\Delta ,-b^2/\Delta$, with $\pm b$ added for electron spin. The displayed square-root expression also handles $b$ comparable to $\Delta$, provided coupling to other principal shells stays negligible. The $2s$ orbital retains zero orbital correction.

These quadratic orbital estimates keep the enhanced contribution from mixing the split $2p$ levels. Minimal magnetic minimal coupling also produces $e^2{B}^2{r}_{\perp }^2/(8m_e)$; its expectation value is positive and must be added for a full order-$B^2$ calculation. For example it gives $e^2{B}^2{a}_0^2/(4m_e)$ for $1s$. It is parametrically smaller than the $2p$ mixing term when $\epsilon \ll \mathrm{Ry}$.

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.