Let the dimensionful angular momentum operators obey and take the interaction Hamiltonian as . Since
the energy eigenvalues at fixed are
where . Subtraction gives the Landé interval rule
Many atomic conventions use dimensionless angular momentum operators and call the energy-valued constant itself ; then the right-hand side is . Each energy level has magnetic sublevels with the same energy in zero field.
For fine structure, the effective interaction is 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, , and the interval between adjacent energy levels is . 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 electrons, orbital magnetic fields, and the dipolar field of electron spin. Projected onto one electronic energy level, their rotationally invariant magnetic-dipole part has the form . The labels are , together with the approximate electronic labels such as . 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 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, . General electrostatic atomic term separations need not obey a single Landé interval rule as varies.

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