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Asymptotic properties of the exchange energy density and the exchange potential of finite systems: relevance for generalized gradient approximations

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Zeitschrift für Physik D Atoms, Molecules and Clusters

Abstract

It is shown that generalized gradient approximations (GGAs) for exchange only, due to their very limited form, quite generally can not simultaneously reproduce both the asymptotic forms of the exchange energy density and the exchange potential of finite systems. Furthermore, mechanisms making GGAs formally approach at least one of these asymptotic forms do not improve the corresponding quantity in the relevant part of the asymptotic regime of atoms. By constructing a GGA which leads to superior atomic exchange energies compared to all GGAs heretofore but does not reproduce the asymptotic form of the exact exchange energy density it is demonstrated that this property is not important for obtaining extremely accurate atomic exchange energies. We conclude that GGAs by their very concept are not suited to reproduce these asymptotic properties of finite systems. As a byproduct of our discussion we present a particularly simple and direct proof of the well known asymptotic structure of the exchange potential of finite spherical systems.

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Author notes

  1. E. Engel

    Present address: Institut für Theoretische Physik, Universität Frankfurt, Robert Mayer Strasse 8–10, W-6000, Frankfurt Main 11, Germany

Authors and Affiliations

  1. Department of Physics, University of Toronto, M5S 1A7, Toronto, Ontario, Canada

    E. Engel, J. A. Chevary, L. D. Macdonald & S. H. Vosko

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  1. E. Engel
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  2. J. A. Chevary
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  3. L. D. Macdonald
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  4. S. H. Vosko
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Engel, E., Chevary, J.A., Macdonald, L.D. et al. Asymptotic properties of the exchange energy density and the exchange potential of finite systems: relevance for generalized gradient approximations. Z Phys D - Atoms, Molecules and Clusters 23, 7–14 (1992). https://doi.org/10.1007/BF01436696

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