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Atomic Term Symbols

An atomic term symbol is a compact label for angular momentum, spin multiplicity, and often parity. In its familiar Russell–Saunders form,

2S+1LJ,{}^{2S+1}L_J,

it can identify an entire pattern of magnetic behavior and transition constraints in a few characters. It is not a wavefunction, an electron configuration, or a guarantee that LL and SS are exact quantum numbers.

The notation is useful precisely because it records a controlled approximation. A good reader should be able to decode a symbol, test whether its angular momenta are mutually consistent, recover parity from the configuration, and recognize when configuration or coupling admixture makes the label approximate.

This page owns the working language of atomic terms and levels: multiplicity, orbital and total angular momentum, parity, magnetic states, and the distinction between LSLS and jjjj notation. Electron Configurations owns subshell occupations, Aufbau reasoning, closed-shell notation, and configuration mixing. Angular Momentum Coupling Schemes owns the general basis-choice logic. LS Coupling owns the atomic Russell–Saunders regime, while jj Coupling owns relativistic-subshell labels, equivalent-electron restrictions, and diagnostics for the complementary limit. Hund’s Rules owns approximate energy ordering among allowed free-atom terms and levels. Fine Structure owns the energy splitting within a term, and Atomic Selection Rules owns the use of these labels in transition problems.

Deriving every allowed term of an equivalent-electron configuration is a separate many-electron problem. It requires antisymmetry, parentage, and configuration-state functions; the relevant foundations are Pauli Exclusion Principle, Spin and Spatial Wavefunctions, and Slater Determinants. Slater Determinants in Atoms gives the practical determinant-to-CSF construction. Here those results are used to interpret labels rather than rederived in full.

Atomic spectroscopy uses a hierarchy of labels. The distinctions matter because different interactions resolve different layers.

ObjectLabels in an LSLS descriptionWhat is grouped together
configurationC=(n1ℓ1)N1(n2ℓ2)N2⋯\mathcal C=(n_1\ell_1)^{N_1}(n_2\ell_2)^{N_2}\cdotsstates with the same orbital occupations
termγC  2S+1Lπ\gamma\mathcal C\;{}^{2S+1}L^{\pi}states with common LL, SS, and parity
levelγC  2S+1LJπ\gamma\mathcal C\;{}^{2S+1}L^{\pi}_Ja fixed total electronic JJ
magnetic state$\gamma\mathcal C LSJM_J\rangle$

The auxiliary label γ\gamma stands for whatever else is needed to distinguish repeated terms: parent terms, seniority, configuration labels, or an enumeration index. In informal usage, “term symbol” often means the full level label including JJ. Strictly, 2S+1L{}^{2S+1}L denotes a term and the subscript JJ selects one fine-structure level of that term.

A helium 1s2p configuration separates into singlet and triplet terms, and the triplet separates into three fine-structure levels.

The 1s2p1s2p configuration has 1212 spin-orbital states. In LSLS coupling they separate into a three-state 1P∘{}^1P^\circ term and a nine-state 3P∘{}^3P^\circ term. The latter contains J=0,1,2J=0,1,2 levels with 11, 33, and 55 magnetic states, respectively.

The hierarchy also clarifies terminology for spectral features. A transition array connects configurations, a multiplet connects terms, a line connects levels, and a resolved Zeeman or hyperfine component connects individual states. Real spectra do not always resolve every layer.

A sufficiently explicit label may be written schematically as

γ C  2S+1LJπ.\gamma\,\mathcal C\; {}^{2S+1}L^{\pi}_J.

Each piece answers a different question:

SymbolMeaningTypical check
C\mathcal Cdominant electron configurationoccupations obey Pauli exclusion
2S+12S+1spin multiplicityS=(multiplicity−1)/2S=(\text{multiplicity}-1)/2
LLtotal electronic orbital angular momentumcapital letter maps to a nonnegative integer
JJtotal electronic angular momentum$
π\pitotal electronic parityπ=(−1)∑iℓi\pi=(-1)^{\sum_i\ell_i} for a configuration
γ\gammaadditional ancestry or state identifierneeded when the other labels recur

Nuclear spin is not included. Coupling electronic JJ to nuclear II produces hyperfine FF, treated on Hyperfine Structure. Likewise, MJM_J labels a magnetic substate but is normally omitted from the zero-field level name.

In LSLS coupling, individual orbital and spin angular momenta are added separately:

L=∑iℓi,S=∑isi,J=L+S.\begin{aligned} \mathbf L&=\sum_i\mathbf \ell_i,\\ \mathbf S&=\sum_i\mathbf s_i,\\ \mathbf J&=\mathbf L+\mathbf S. \end{aligned}

The corresponding eigenvalues are

L2=ℏ2L(L+1),S2=ℏ2S(S+1),J2=ℏ2J(J+1).\begin{aligned} \mathbf L^2&=\hbar^2L(L+1),\\ \mathbf S^2&=\hbar^2S(S+1),\\ \mathbf J^2&=\hbar^2J(J+1). \end{aligned}

For fixed LL and SS, angular-momentum addition permits

J=∣L−S∣,∣L−S∣+1,ldots,L+S.J=|L-S|, |L-S|+1,ldots,L+S.

Each JJ level contains

2J+12J+1

magnetic states before hyperfine interactions or external fields are resolved. Across the complete LSLS term,

∑J=∣L−S∣L+S(2J+1)=(2L+1)(2S+1).\sum_{J=|L-S|}^{L+S}(2J+1) =(2L+1)(2S+1).

This identity is an excellent consistency check: changing from the uncoupled ∣LML;SMS⟩|LM_L;SM_S\rangle basis to the coupled ∣LS;JMJ⟩|LS;JM_J\rangle basis cannot change the dimension of the space.

The total orbital quantum number is written as a capital letter:

LL01234567
term letterSSPPDDFFGGHHIIKK

The letter JJ is skipped in this sequence to avoid confusion with total angular momentum. Lowercase s,p,d,f,…s,p,d,f,\ldots labels a one-electron subshell with angular momentum ℓ\ell; uppercase S,P,D,F,…S,P,D,F,\ldots labels the total LL of all electrons. Thus a p2p^2 configuration can contain an SS, PP, or DD term.

The symbol 4F9/2{}^4F_{9/2}, for example, means

S=32,L=3,J=92.S=\frac{3}{2}, \qquad L=3, \qquad J=\frac{9}{2}.

The J=9/2J=9/2 level has 2J+1=102J+1=10 magnetic states. It is one member of an FF term whose allowed JJ values are 3/23/2, 5/25/2, 7/27/2, and 9/29/2.

The left superscript is

2S+1,2S+1,

called the spin multiplicity. Common names are

SS2S+12S+1Name
0011singlet
1/21/222doublet
1133triplet
3/23/244quartet
2255quintet

Multiplicity counts the possible MSM_S values of spin SS. It does not generally equal the number of magnetic states of a level, which is 2J+12J+1. It also need not equal the number of JJ levels in a term: the latter is

2min⁡(L,S)+1.2\min(L,S)+1.

Only when L≥SL\geq S does that number equal 2S+12S+1. For instance, 5S{}^5S has multiplicity five but only one level, 5S2{}^5S_2, because L=0L=0 forces J=S=2J=S=2.

Each one-electron orbital has parity (−1)ℓ(-1)^\ell. A configuration therefore has total electronic parity

π=∏i(−1)ℓi=(−1)∑iℓi.\pi =\prod_i(-1)^{\ell_i} =(-1)^{\sum_i\ell_i}.

Closed subshells contribute even parity, so in practice only open subshells need to be counted. Standard atomic notation usually leaves even parity unmarked and appends a degree sign to an odd-parity term:

3P2even parity,3P2∘odd parity.\begin{aligned} {}^3P_2 &\quad &&\text{even parity},\\ {}^3P^\circ_2 &\quad &&\text{odd parity}. \end{aligned}

Databases may use an asterisk in plain-text output because a superscript degree sign is unavailable. Some tables instead print explicit ee and oo parity labels, especially when no reliable LSLS assignment exists.

The term letter does not determine parity. Two pp electrons give

π(p2)=(−1)1+1=+1,\pi(p^2)=(-1)^{1+1}=+1,

so a p2  3PJp^2\;{}^3P_J level is even. By contrast, an sp  3PJ∘sp\;{}^3P^\circ_J level is odd because 0+10+1 is odd. Confusing the letter PP with parity is one of the most common notation errors.

For the usual electromagnetic atomic Hamiltonian, parity and JJ often remain exact even when configuration mixing makes LL and SS approximate. External electric fields can mix opposite parities; Stark Effect in Atoms develops that failure mode.

Helium shows how configuration, antisymmetry, terms, and levels fit together.

The 1s21s^2 ground configuration has L=0L=0 and even parity. Because both electrons occupy the same spatial orbital, Pauli antisymmetry permits only the spin singlet. The level is

1s2  1S0.1s^2\;{}^1S_0.

A hypothetical 1s2  3S11s^2\;{}^3S_1 would have a symmetric spin state and the same symmetric spatial occupation, so it is excluded.

The electrons occupy nonequivalent orbitals, and both spin couplings occur:

1s2s  1S0,1s2s  3S1.1s2s\;{}^1S_0, \qquad 1s2s\;{}^3S_1.

Both are even because ell1s+ell2s=0ell_{1s}+ell_{2s}=0. Exchange and correlation give the singlet and triplet different energies; that energy ordering is not encoded in the symbols themselves.

Here L=1L=1 and parity is odd. The allowed terms and levels are

1s2p  1P1∘,1s2p  3P0,1,2∘.\begin{aligned} 1s2p\;{}^1P^\circ_1, \qquad 1s2p\;{}^3P^\circ_{0,1,2}. \end{aligned}

The singlet contributes 2J+1=32J+1=3 magnetic states. The triplet contributes 1+3+5=91+3+5=9, accounting for all 1212 states of the configuration. In a pure LSLS model, electric-dipole transitions approximately conserve SS, which is why singlet and triplet systems have sharply different line strengths. The precise hierarchy of exact and approximate rules is given in Atomic Selection Rules.

An alkali atom has one valence electron outside closed subshells. The core has L=S=J=0L=S=J=0 and even parity, so the term labels reduce to those of the valence electron:

ns⟶ns  2S1/2,np⟶np  2P1/2,3/2∘,nd⟶nd  2D3/2,5/2.\begin{array}{ccl} ns &\longrightarrow& ns\;{}^2S_{1/2},\\ np &\longrightarrow& np\;{}^2P^{\circ}_{1/2,3/2},\\ nd &\longrightarrow& nd\;{}^2D_{3/2,5/2}. \end{array}

The sodium ground level, for example, is 3s  2S1/23s\;{}^2S_{1/2}. Its resonance-line upper configuration 3p3p produces the two fine-structure levels 3p  2P1/2∘3p\;{}^2P^{\circ}_{1/2} and 3p  2P3/2∘3p\;{}^2P^{\circ}_{3/2}. Their separation is the familiar alkali doublet. Alkali Atoms explains the effective one-electron picture, while Fine Structure develops the splitting mechanism.

This simplicity is special. For multiple open subshells, the same configuration can support several LL and SS values, and equivalent-electron antisymmetry removes some combinations that naive vector addition would allow.

Pauli Principle in Atoms derives the exchange-parity restriction that selects the allowed terms. Here the result is used as a notation and state-counting check.

For a p2p^2 configuration, one pp subshell contains six spin-orbitals. Choosing two gives

(62)=15\binom{6}{2}=15

antisymmetric determinants. The allowed LSLS levels are

1S0,1D2,3P0,1,2.{}^1S_0, \qquad {}^1D_2, \qquad {}^3P_{0,1,2}.

Their magnetic-state counts are

1+5+(1+3+5)=15.1+5+(1+3+5)=15.

The count closes, and every term has even parity because the two pp electrons contribute (−1)2(-1)^2. This example is useful as a diagnostic, but it does not replace the antisymmetrized construction that determines which terms survive.

LS Coupling, jj Coupling, and Intermediate Coupling

Section titled “LS Coupling, jj Coupling, and Intermediate Coupling”

The superscript-multiplicity notation assumes that LL and SS are useful labels. That is most natural when residual electrostatic interactions organize the spectrum more strongly than individual-electron spin–orbit interactions.

RegimeCoupling orderNatural label
LSLS coupling∑iℓi→L\sum_i\mathbf\ell_i\to\mathbf L, ∑isi→S\sum_i\mathbf s_i\to\mathbf S, then L+S→J\mathbf L+\mathbf S\to\mathbf JγC  2S+1LJπ\gamma\mathcal C\;{}^{2S+1}L^\pi_J
jjjj couplingeach ℓi+si→ji\mathbf\ell_i+\mathbf s_i\to\mathbf j_i, then ∑iji→J\sum_i\mathbf j_i\to\mathbf Jconfiguration with jij_i subscripts and coupled JJ
intermediate couplingdiagonalize across several basis labels with the same exact symmetriesdominant-component label plus composition data

A schematic two-electron jjjj basis is

∣(ℓ1s1)j1,(ℓ2s2)j2;JMJ⟩.\left| (\ell_1s_1)j_1, (\ell_2s_2)j_2; JM_J \right\rangle .

For example, a closed pair in a relativistic p1/2p_{1/2} subshell may be labeled (p1/2 2)0(p_{1/2}^{\,2})_0. There is no generally useful spin multiplicity in that label because LL and SS are not coupled first. The full construction and its Pauli restrictions are developed in jj Coupling.

Real atoms often lie between the limits. A level of exact JJ and parity may have an expansion

∣ΨJπ⟩=∑rcr∣γrCrLrSr;Jπ⟩.|\Psi_{J\pi}\rangle = \sum_r c_r |\gamma_r\mathcal C_rL_rS_r;J\pi\rangle .

If one weight ∣cr∣2|c_r|^2 dominates, its LSLS term is a useful short name. If several weights are comparable, a single symbol hides important physics: nominally spin-forbidden lines can gain strength, Landé factors shift away from pure-LSLS values, and labels may exchange character through an avoided crossing. The Hamiltonian has not changed when the basis notation changes; only the most informative description has.

Use the following sequence when reading a table or assigning a calculated level:

  1. Write the configuration. Check occupations and identify closed versus open subshells.
  2. Compute parity. Evaluate (−1)∑iℓi(-1)^{\sum_i\ell_i} and compare it with the printed degree sign, asterisk, or e/oe/o label.
  3. Identify the coupling scheme. Do not decode a jjjj label as though it were an LSLS symbol.
  4. Decode multiplicity and LL. Recover SS from 2S+12S+1 and map the capital letter to LL.
  5. Test JJ. Require ∣L−S∣≤J≤L+S|L-S|\leq J\leq L+S in unit steps.
  6. Apply equivalent-electron restrictions. Vector addition alone does not enforce Pauli antisymmetry.
  7. Distinguish term, level, and state. Add JJ for a level and MJM_J only for a magnetic state.
  8. Inspect composition when precision matters. A database assignment may identify the leading eigenvector component rather than an exact L,SL,S eigenstate.

The NIST Atomic Spectra Database reports configurations, terms, JJ, and level energies separately. That separation is valuable: it prevents a compact term label from being mistaken for a complete state specification and makes uncertain assignments visible.

  • Reading lowercase pp and uppercase PP as the same object.
  • Calling 2S+12S+1 the degeneracy of a JJ level.
  • Assuming a PP term has odd parity.
  • Omitting the configuration when several configurations contain the same term.
  • Treating every angular-momentum sum as Pauli-allowed for equivalent electrons.
  • Assuming 2S+1LJ{}^{2S+1}L_J fixes the energy ordering; Hund’s Rules are additional approximations.
  • Treating LL and SS as exact in a strongly mixed or relativistic spectrum.
  • Putting nuclear FF or its projection into the electronic term symbol.
  • Losing the odd-parity degree sign when transcribing a database’s plain-text output.

Decode 4F9/2∘{}^4F^{\circ}_{9/2}. Give SS, LL, JJ, parity, the allowed JJ values of the term, and the number of magnetic states in the displayed level.

Solution

The multiplicity gives

2S+1=4⟹S=32.2S+1=4 \quad\Longrightarrow\quad S=\frac{3}{2}.

The letter FF means L=3L=3, and the subscript gives J=9/2J=9/2. The degree sign marks odd parity. Angular-momentum addition permits

J=∣3−32∣,ldots,3+32=32,52,72,92.J=\left|3-\frac32\right|,ldots, 3+\frac32 = \frac32,\frac52,\frac72,\frac92.

The displayed J=9/2J=9/2 level has

2J+1=102J+1=10

magnetic states.

Exercise 2: Multiplicity is not level degeneracy

Section titled “Exercise 2: Multiplicity is not level degeneracy”

Compare 5S2{}^5S_2 and 3P2{}^3P_2. State the multiplicity, number of fine-structure JJ levels in the complete term, and number of MJM_J states in the displayed level.

Solution

For 5S2{}^5S_2, S=2S=2 and L=0L=0. The multiplicity is five, but only J=2J=2 is possible, so the term has one fine-structure level. That level has 2J+1=52J+1=5 magnetic states.

For 3P2{}^3P_2, S=1S=1 and L=1L=1. Its multiplicity is three and the complete term has J=0,1,2J=0,1,2, hence three fine-structure levels. The displayed J=2J=2 level has five magnetic states. The same number five appears for two different reasons in these examples.

Show that the 1s2p  1P1∘1s2p\;{}^1P^\circ_1 and 1s2p  3P0,1,2∘1s2p\;{}^3P^\circ_{0,1,2} levels account for all product states with one electron in 1s1s and one in 2p2p.

Solution

The 1s1s orbital supplies two spin-orbitals. The 2p2p subshell supplies 33 orbital projections times 22 spin projections, or six spin-orbitals. With one electron in each subshell, there are

2×6=122\times6=12

states. The singlet PP term has only J=1J=1 and contributes 2J+1=32J+1=3 states. The triplet PP term contributes

N3P=∑J=02(2J+1)=1+3+5=9.\begin{aligned} N_{{}^3P} &=\sum_{J=0}^{2}(2J+1)\\ &=1+3+5=9. \end{aligned}

Thus 3+9=123+9=12. All levels are odd because the configuration has parity (−1)0+1=−1(-1)^{0+1}=-1.

Exercise 4: Parity of a p-squared configuration

Section titled “Exercise 4: Parity of a p-squared configuration”

A table lists the levels p2  1S0p^2\;{}^1S_0, p2  1D2p^2\;{}^1D_2, and p2  3P0,1,2p^2\;{}^3P_{0,1,2}. Determine their parity and verify that their magnetic-state count matches the number of two-electron determinants in a pp subshell.

Solution

Two pp electrons have

π=(−1)1+1=+1,\pi=(-1)^{1+1}=+1,

so all listed levels are even despite the PP term letter. A pp subshell has six spin-orbitals, giving

(62)=15\binom{6}{2}=15

determinants. The singlet SS level contributes one magnetic state, the singlet DD level contributes five, and the triplet PP levels contribute 1+3+5=91+3+5=9. Their sum is 1+5+9=151+5+9=15.

Write the LSLS level labels and parities for an alkali valence electron in nsns, npnp, and ndnd orbitals, assuming an even-parity closed core.

Solution

The valence spin is S=1/2S=1/2, so every term is a doublet. The closed core contributes no angular momentum. Therefore

ns:2S1/2even,np:2P1/2,3/2∘odd,nd:2D3/2,5/2even.\begin{array}{ccl} ns &:& {}^2S_{1/2}\quad\text{even},\\ np &:& {}^2P^{\circ}_{1/2,3/2}\quad\text{odd},\\ nd &:& {}^2D_{3/2,5/2}\quad\text{even}. \end{array}

The parity follows from (−1)ℓ(-1)^\ell, and the two levels for ell>0ell>0 have J=ℓ±1/2J=\ell\pm1/2.

Suppose a normalized odd-parity J=1J=1 eigenstate is approximated by

∣Ψ⟩=0.82  ∣1P1∘⟩+0.18  ∣3P1∘⟩.|\Psi\rangle = \sqrt{0.82}\;|{}^1P^\circ_1\rangle + \sqrt{0.18}\;|{}^3P^\circ_1\rangle.

Which labels are exact in a rotationally and parity-invariant Hamiltonian, and how should the level be named?

Solution

Both basis components have J=1J=1 and odd parity, so those labels can remain exact. The state is not an eigenstate of S2S^2: singlet and triplet are approximate component labels. If a short LSLS name is needed, the dominant-component convention gives 1P1∘{}^1P^\circ_1, accompanied by the composition 82%82\% singlet and 18%18\% triplet. Omitting the composition would hide the mechanism that can open an intercombination transition.

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