In atomic physics, hyperfine structure is defined by small shifts in otherwise degenerate energy levels and the resulting splittings in those energy levels of atoms, molecules, and ions, due to electromagnetic multipole interaction between the nucleus and electron clouds.
In atoms, hyperfine structure arises from the energy of the nuclear magnetic dipole moment interacting with the magnetic field generated by the electrons and the energy of the nuclear electric quadrupole moment in the electric field gradient due to the distribution of charge within the atom. Molecular hyperfine structure is generally dominated by these two effects, but also includes the energy associated with the interaction between the magnetic moments associated with different magnetic nuclei in a molecule, as well as between the nuclear magnetic moments and the magnetic field generated by the rotation of the molecule.
Hyperfine structure contrasts with fine structure, which results from the interaction between the magnetic moments associated with electron spin and the electrons' orbital angular momentum. Hyperfine structure, with energy shifts typically orders of magnitudes smaller than those of a fine-structure shift, results from the interactions of the nucleus (or nuclei, in molecules) with internally generated electric and magnetic fields.
The first theory of atomic hyperfine structure was given in 1930 by Enrico Fermi
for an atom containing a single valence electron with an arbitrary angular momentum. The Zeeman splitting of this structure was discussed by S. A. Goudsmit and R. F. Bacher later that year.
In 1935, H. Schüler and Theodor Schmidt proposed the existence of a nuclear quadrupole moment in order to explain anomalies in the hyperfine structure.
The theory of hyperfine structure comes directly from electromagnetism, consisting of the interaction of the nuclear multipole moments (excluding the electric monopole) with internally generated fields. The theory is derived first for the atomic case, but can be applied to each nucleus in a molecule.
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