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    Pauli Approximation in Many-Electron Atoms

    John Detrich

    • Laboratory of Molecular Structure and Spectra, Department of Physics, University of Chicago, Chicago, Illinois 60637

    Phys. Rev. A 5, 2014 – Published 1 May, 1972

    DOI: https://doi.org/10.1103/PhysRevA.5.2014

    Abstract

    The Pauli approximation for many-electron atoms is derived. This yields an unambiguous expression for the fine-structure splitting and other first-order relativistic corrections to the energy, using nonrelativistic wave functions. A formalism is developed for atoms, based on these results, which is suitable for the evaluation of the fine structure using multiconfiguration wave functions. Fine-structure splittings calculated from Hartree-Fock wave functions are presented for ground states from He through Ar; the remaining energy corrections are also presented. Multiconfiguration results are presented for the lowest D2 and P2 states of N, accounting for about 80% of the discrepancy between Hartree-Fock values and experimental values.

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