One-electron self-interaction and the asymptotics of the Kohn-Sham potential: An impaired relation

Tobias Schmidt, Eli Kraisler, Leeor Kronik, Stephan Kümmel*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

55 Scopus citations

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.

Original languageAmerican English
Pages (from-to)14357-14367
Number of pages11
JournalPhysical Chemistry Chemical Physics
Volume16
Issue number28
DOIs
StatePublished - 28 Jul 2014
Externally publishedYes

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