Codex @codex  0

A level of an atomic term with specified total angular momentum $J$. Without an external field, its $2J+1$ magnetic states remain degenerate in a rotationally invariant Hamiltonian.

An atomic term with total spin one half and spin multiplicity two. A doublet S term has only J=1/2, while a doublet with nonzero L can have J=L-1/2 and J=L+1/2. Spin multiplicity therefore need not equal the number of resolved spectral lines.

Tabulated strontium electron configurations, atomic terms, total angular momentum and energy levels in $\mathrm{c}{\mathrm{m}}^{-1}$. Multiplication by $100$ converts to ${\mathrm{m}}^{-1}$. The entries for $5s5p$ and $5s6s$ independently test assignments inferred from rounded optical wavelengths.

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.

The $4f^7$ shell carries a large spin (its ground atomic term under Hund's rules has $L=0,S=7/2$), and the $6s$ electron penetrates the inner shells. Its nonzero probability density at the atomic nucleus supplies a potentially large Fermi contact interaction with the nuclear magnetic dipole moment. The $6s$ shell here is singly occupied, so the obligatory paired-$6s^2$ cancellation is absent. Both stable europium isotopes have nonzero nuclear spin, as the spectrum below also establishes.

The term symbol ${}^8{D}_{11/2}$ specifies $S=7/2$, $L=2$, $J=11/2$. Its large $J$, combined with appreciable nuclear spin, permits a wide range of total angular momentum $F$ and hence a substantial total hyperfine structure span. For $I=5/2$, $F=3,\dots ,8$ and the span is $30|a|$. The penetrating $6s$ contribution and the available range of $F$ explain the large hyperfine structure; the term symbol alone does not determine its constant, which also depends on electronic recoupling, radial wavefunctions and configuration interaction.

Closed subshells have $L=S=0$, so only the open $p$ or $d$ subshell determines each atomic term. Apply Hund's rules in order: maximize $S$, maximize $L$ at that $S$, then choose the lowest $J$ below half filling or the highest $J$ above half filling.

For carbon, the two $2p$ electrons occupy different magnetic atomic orbitals with parallel spins, giving $S=1$. Their largest allowed $M_L$ at that spin is $1+0=1$, so $L=1$, a $P$ term. The $p^2$ subshell is less than half full, giving $J=|1-1|=0$. The ground level is ${}^3{P}_0$.

For vanadium, three parallel-spin $3d$ electrons give $S=3/2$. The largest $M_L$ compatible with the Pauli exclusion principle is $2+1+0=3$, hence $L=3$, an $F$ term. The $d^3$ subshell is less than half full, so $J=3-3/2=3/2$. The ground level is ${}^4{F}_{3/2}$.

For cobalt, the $d^7$ subshell is equivalent to three $d$ holes for the allowed $L,S$ terms, so its maximum-spin, maximum-$L$ term is again ${}^{4}F$. Explicitly, five spin-up electrons fill all $m_l$ values and two spin-down electrons can occupy $m_l=2,1$, giving $M_S=3/2$ and $M_L=3$. Since $d^7$ is more than half full, $J=3+3/2=9/2$. The ground level is ${}^4{F}_{9/2}$.

An electron configuration specifies the occupied one-electron subshells and their populations, such as $1s^{2}2s^{2}2p^2$, without fixing how all orbital and spin angular momenta are coupled.

An atomic term groups states of a configuration with the same $L$ and $S$. An atomic fine-structure level additionally specifies $J$; spin-orbit coupling can split one term into several such levels. In zero external field, a level retains $2J+1$ magnetic substates.

The term symbol iswith letters $S,P,D,F,G,\dots$ denoting $L=0,1,2,3,4,\dots$. The superscript is the spin multiplicity. Without the $J$ subscript, ${}^{2S+1}L$ identifies an atomic term, rather than an individual fine-structure level.

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 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.