Some thoughts about the stability and reliability of commonly used exchange-correlation functionals - coverage of dynamic and nondynamic correlation effects

被引：113

作者：

Polo, V ^{[1
]}

Kraka, E ^{[1
]}

Cremer, D ^{[1
]}

机构：

[1] Univ Gothenburg, Dept Theoret Chem, S-41320 Gothenburg, Sweden

来源：

THEORETICAL CHEMISTRY ACCOUNTS | 2002年 / 107卷 / 05期

关键词：

DFT; self-interaction error; SIC-DFT; exchange effects; correlation effects; long-range correlation;

D O I：

10.1007/s00214-002-0331-4

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The self-interaction error (SIE) of commonly used density functional theory (DFT) exchange functionals mimics long-range (nondynamic) pair correlation effects in an unspecified way. Slater exchange suffers from a larger SIE and, therefore, covers more nondynamic correlation effects than Becke exchange, which is the reason why exchange-correlation (XC) functionals based on Slater exchange lead to stabler restricted DFT solutions than those based on Becke exchange. However, the stability of an XC functional does not guarantee higher accuracy. On the contrary, if system-specific nondynamic correlation effects have to be introduced via the form of the wave function, these will be suppressed by nondynamic correlation effects already covered by the exchange functional. Hybrid functionals suffer less from the SIE and, therefore, cover a smaller number of nondynamic electron correlation effects. Accordingly, they are better suited when nondynamic electron correlation has to be introduced by the form of the wave function. It is shown that, for example, broken-symmetry unrestricted DFT calculations are more accurate when carried out with B3LYP than BLYP contrary to claims made in the literature.

引用

页码：291 / 303

页数：13

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