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Issue 28, 2014
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One-electron self-interaction and the asymptotics of the Kohn–Sham potential: an impaired relation

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Abstract

One-electron self-interaction and an incorrect asymptotic behavior of the Kohn–Sham exchange–correlation potential are among the most prominent limitations of many present-day density functionals. However, a one-electron self-interaction-free energy does not necessarily lead to the correct long-range potential. This is shown here explicitly for local hybrid functionals. Furthermore, carefully studying the ratio of the von Weizsäcker kinetic energy density to the (positive) Kohn–Sham kinetic energy density, τW/τ, reveals that this ratio, which frequently serves as an iso-orbital indicator and is used to eliminate one-electron self-interaction effects in meta-generalized-gradient approximations and local hybrid functionals, can fail to approach its expected value in the vicinity of orbital nodal planes. This perspective article suggests that the nature and consequences of one-electron self-interaction and some of the strategies for its correction need to be reconsidered.

Graphical abstract: One-electron self-interaction and the asymptotics of the Kohn–Sham potential: an impaired relation

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Publication details

The article was received on 24 Dec 2013, accepted on 19 Feb 2014 and first published on 20 Feb 2014


Article type: Perspective
DOI: 10.1039/C3CP55433C
Phys. Chem. Chem. Phys., 2014,16, 14357-14367
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    One-electron self-interaction and the asymptotics of the Kohn–Sham potential: an impaired relation

    T. Schmidt, E. Kraisler, L. Kronik and S. Kümmel, Phys. Chem. Chem. Phys., 2014, 16, 14357
    DOI: 10.1039/C3CP55433C

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