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Theory of One Electron Binding Energies Including Correlation, Relativistic and Radiative Effects: Application to Free Atoms and Metals

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Excited States in Quantum Chemistry

Part of the book series: NATO Advanced Study Institutes Series ((ASIC,volume 46))

Abstract

The recent emphasis on non rare-gas core Binding Energies (BE) measurements and the continued use of these BE to probe bulk and surface properties makes this a timely subject to review. The wide range of atoms treated and the accuracies required place stringent demands on any comprehensive theory, forcing it to consider effects of relaxation, relativity, radiation, correlation, nuclear size and the bulk. To date, there is no theory capable of treating these simultaneously, although we suggest a means by which relativistic and correlation effects may eventually be unified. This would leave proper treatment of bulk effects as the prominent challenge.

The existing additive theory is reviewed and extended to include a way of making a priori determinations of when and what correlation effects are large. This allows assessment of experimental observations and of independent particle model results and eases computation of correlation effects. A simple method of including the significant radiative effects is also put forth. This theory has been applied to the 1s BE of C, O, O-, F, F-, Ne, Na, Na+ in excellent agreement with experiment (~ 0.1–0.2 eV), to all core subshells of K, (accuracies ~ 0.1–0.5 eV), and to selected subshells of Cs. Modifying Shirley’s ad hoc model for “extra atomic relaxation”, which we suggest has considerable utility, we produce metallic BE which agree with measured values to within 1–2 eV.

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  1. Theoretical Chemistry Institute, National Hellenic Research Foundation, Athens 501/1, Greece

    Donald R. Beck & Cleanthes A. Nicolaides

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Beck, D.R., Nicolaides, C.A. (1978). Theory of One Electron Binding Energies Including Correlation, Relativistic and Radiative Effects: Application to Free Atoms and Metals. In: Nicolaides, C.A., Beck, D.R. (eds) Excited States in Quantum Chemistry. NATO Advanced Study Institutes Series, vol 46. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-9902-2_12

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  • DOI: https://doi.org/10.1007/978-94-009-9902-2_12

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