Abstract
Sternheimer ionic antishielding factors, γ∞, have been calculated for F−, Cl−, Br−, and I− in crystals using the Watson model within the nonrelativistic Hartree-Fock approximation and the perturbation numerical procedure. The free ion calculations of γ∞ using the Hartree-Fock wave functions have also been carried out in order to ascertain the solid-state effects. The free ion values of γ∞ change from −22.2, −55.1, −135.106, and −248.1 to −10.3, −34.8, −75.6, and −148.7 in solids for F−, Cl−, Br−, and I−, respectively. A major part of the discrepancy between the free ionic γ∞ values based on the Hartree-Fock and Hartree-Fock-Slater wave functions, as noted by the previous workers, is shown to arise from an inaccurate description of the self-interaction potential in the conventional Slater exchange approximation.
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Dedicated to Prof. Dr. H. Hartmann on the occasion of his sixty-fifth birthday.
Alexander von Humboldt fellow, on leave of absence from the University of Hyderabad, India.
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Sen, K., Weiss, A. Sternheimer antishielding factors of F−, Cl−, Br− and I− . Theoret. Chim. Acta 52, 181–187 (1979). https://doi.org/10.1007/BF00547677
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DOI: https://doi.org/10.1007/BF00547677