Analysis of fine-structure excitation energies in Dirac-Fock and perturbation theories

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Abstract
The authors compare total fine structure and its components predicted by Dirac-Fock calculations for light atoms with those predicted by perturbation treatments of relativistic effects. An apparent anomaly in the properties of the valence Dirac-Fock orbitals found in optimal level calculations for the fluorine atom is explained by the greater electrostatic repulsion between a pair of electrons in the 2p orbital compared with a pair in the 2p orbital. It is explained why the components of the fine structure in perturbation theory do not reproduce their Dirac-Fock counterparts. It is shown that the fine structure in atoms containing only one valence electron can be interpreted in terms of the difference in the electrostatic potential energies of the small components of the valence Dirac-Fock atomic orbitals, provided core-valence exchange is neglected.

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