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With $J=4$, the measured effective paramagnetic moment gives the Landé g-factorFor the free-ion Hund's rules values $S=1$, $L=5$, $J=4$, the stated formula yieldsThusThe source fit is consistent with the unquenched $4f$ orbital magnetic moment of the free praseodymium ion, within graphical accuracy. Small deviations need not indicate a change of electron configuration: crystal field splitting, interactions and the fit range can affect a measured magnetic susceptibility.

The given electron configuration has an inert closed $[\mathrm{Xe}]$ core and two $4f$ electrons. The Aufbau principle identifies the occupied subshells; the free-ion term within the open $4f^2$ configuration is then selected by Hund's rules. A closed core contributes $L=S=0$.

Each $f$ electron has orbital angular momentum quantum number $l=3$. Place the two spins parallel, so $S=1$. The Pauli exclusion principle then requires distinct orbital projections. The largest allowed total projection is $M_L=3+2=5$, obtained from $m_l=3$ and $m_l=2$, giving the maximum allowed $L=5$. A larger $M_L=6$ would place two parallel-spin electrons in the same atomic orbital and is forbidden.

The $f$ subshell holds fourteen electrons; $f^2$ is less than half filled. The third of Hund's rules therefore selects $J=L-S=4$. HenceThe term symbol uses $2S+1=3$ and the spectroscopic letter $H$ for $L=5$. The praseodymium ion retains an orbital contribution, so a spin-only estimate would be inappropriate.

Hund's rules maximizes total spin within the partially filled shell: parallel spins require an antisymmetric spatial wavefunction, reducing Coulomb overlap through exchange. Among terms with that spin, the second rule selects the largest total orbital angular momentum. The third rule, from spin-orbit coupling within the selected term, gives $J=|L-S|$ below half filling and $J=L+S$ above half filling, with the half-filled case treated directly.

For seven $4f$ electrons, put one parallel-spin electron in each $m_l=-3,-2,-1,0,1,2,3$ orbital. Their orbital projections sum to zero and form the half-filled $L=0$ shell; all seven spins add. ThusThere is no ambiguity from applying the below- or above-half-filled formula because $L=0$. The absence of a first-order orbital moment is important for the weak magnetic anisotropy discussed in c. These are isolated-ion term rules; a crystal field or strong covalency can alter other ions' orbital behavior, but the half-filled Eu${}^{2+}$ shell is unusually robust.

For a partially filled $4f$ shell, the outer $5s$ and $5p$ shells shield the localized orbitals from the ligands. Coulomb interactions establish $L,S$ through Hund's rules, and spin-orbit coupling usually exceeds the much smaller crystal field splitting. First form a ground $J$ multiplet using $\mathbf{J}=\mathbf{L}+\mathbf{S}$, then split that multiplet by the crystal environment. The orbital contribution is therefore generally retained, and the g-factor is a multiplet Landé factor rather than an almost spin-only value. Weak external Zeeman and hyperfine interactions can subsequently resolve the remaining states. Exceptions with $J=0$ or unusual valence require separate treatment.

For a partially filled $3d$ shell, electron–electron Coulomb repulsion and Hund's rules first favour particular total spin and orbital terms. The crystal field splitting is substantial because these orbitals overlap the ligand environment; it normally exceeds the spin-orbit coupling and often quenches the orbital moment. Competition between the splitting and the electron pairing energy determines high-spin versus low-spin filling. A common hierarchy is Coulomb term energies, then crystal-field and Hund-exchange scales, then spin–orbit and weak-field Zeeman energies; the relative sizes of crystal-field splitting and pairing are material-dependent. Hyperfine coupling, if the nucleus carries spin, adds a smaller splitting. An isolated ion has no inter-ion exchange ordering field.

For the regular octahedron, repulsion from the six oxygen ligands raises the two $e_g$ orbitals, $d_{z^2}$ and $d_{x^2-y^2}$, above the three $t_{2g}$ orbitals, $d_{xy},d_{xz},d_{yz}$. The latter point between the metal-ligand axes and experience less direct repulsion. The crystal field splitting is therefore a lower triplet and an upper doublet.

For the $3d^2$ V${}^{3+}$ ion, Hund's rules put the two electrons into different $t_{2g}$ orbitals with parallel spins, giving $S=1$. There are three choices for the unoccupied $t_{2g}$ orbital, so the orbital ground state is triply degenerate. Its spin degeneracy is separate. This orbital degeneracy makes a symmetry-lowering Jahn-Teller effect possible.

The oxygen atom has $1s^{2}2s^{2}2p^4$. Each oxygen contributes six valence electrons, so the molecular diagram contains twelve. Taking the internuclear direction as $z$, the relevant ordering for oxygen isThe valence occupation isThe final two electrons occupy the degenerate antibonding orbitals singly with parallel spin, following Hund's rules. Thus oxygen has two unpaired electrons and is paramagnetic. The $1s$ core orbitals are deliberately omitted from the valence-only molecular orbital diagram.

For nonequivalent p-s and p-p term counting, the closed $3s^2$ shell has $L=S=0$. For $3p4s$, the open orbitals give $L=1$ and $S=0,1$, henceHund's rules predict the order ${}^3{P}_0<{}^3{P}_1<{}^3{P}_2<{}^1{P}_1$.

For $3p4p$, the electrons are in nonequivalent orbitals. All $L=0,1,2$ and $S=0,1$ combinations are allowed:Applying maximum spin first, maximum orbital angular momentum next, and smallest $J$ first for these less-than-half-filled open subshells gives the qualitative orderingThe state counts are $12$ for $3p4s$ and $36$ for $3p4p$. Imposing the equivalent-$p^2$ restrictions would incorrectly discard allowed terms. These are Hund-rule predictions; exact interleavings in a real excited configuration require the actual Coulomb and spin-orbit matrix elements.

Exchange interaction arises from Coulomb interaction together with the antisymmetry required for identical electrons. Different spin states require different spatial symmetry and therefore different pair correlations and Coulomb energy; exchange is not the classical magnetic dipole force between spins. For electrons in distinct atomic orbitals, positive direct exchange favors parallel spins, underlying Hund's rules and the formation of local moments.

In a solid with localized moments, a common convention is $H=-J{\sum }_{⟨ij⟩}{\mathbf{S}}_i\cdot {\mathbf{S}}_j$. Then $J>0$ favors ferromagnetism and $J<0$ favors antiferromagnetism. Superexchange through a ligand and other virtual hopping processes can produce either effective sign depending on orbital occupancy and geometry; half-filled orbitals often give antiferromagnetic coupling. For itinerant electrons, the Stoner criterion describes a competition between exchange energy gain and the kinetic cost of splitting the spin populations.

Experiments distinguish these descriptions through both static and dynamic response. Magnetic neutron diffraction locates magnetic Bragg peaks and therefore the ordering wavevector; an antiferromagnet can have such peaks despite zero bulk moment. Inelastic neutron scattering measures spin-wave dispersion, from which an exchange scale can be fitted. A Curie-Weiss susceptibility intercept gives complementary information about dominant coupling, but its sign alone does not establish the actual ordered structure.

A chemical element of atomic number 59. Its trivalent ion has a $4f^2$ open-shell electron configuration. In LS coupling, Hund's rules select $L=5$, $S=1$, $J=4$, the ${}^3{H}_4$ term symbol. The corresponding free-ion Landé g-factor is $4/5$ and its effective paramagnetic moment is $(4/5)\sqrt{20}{\mu }_B\simeq 3.58{\mu }_B$.