TY - JOUR

T1 - One-electron self-interaction and the asymptotics of the Kohn-Sham potential

T2 - An impaired relation

AU - Schmidt, Tobias

AU - Kraisler, Eli

AU - Kronik, Leeor

AU - Kümmel, Stephan

PY - 2014/7/28

Y1 - 2014/7/28

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84903536867&partnerID=8YFLogxK

U2 - 10.1039/c3cp55433c

DO - 10.1039/c3cp55433c

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AN - SCOPUS:84903536867

SN - 1463-9076

VL - 16

SP - 14357

EP - 14367

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

IS - 28

ER -