Accuracy of Electron Affinities of Atoms in Approximate Density Functional Theory

被引：71

作者：

Lee, Donghyung ^{[1
]}

Furche, Filipp ^{[1
]}

Burke, Kieron ^{[1
]}

机构：

[1] Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2010年 / 1卷 / 14期

基金：

美国国家科学基金会;

关键词：

CORRELATED MOLECULAR CALCULATIONS; GAUSSIAN-BASIS SETS; KOHN-SHAM; EXACT-EXCHANGE; NEGATIVE-IONS; APPLICABILITY;

D O I：

10.1021/jz1007033

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：

Most approximate density functionals do not bind small atomic; anions because of large self interaction errors. Yet atomic electron affinities are often calculated using finite basis sets with surprisingly good results, despite positive highest occupied molecular orbital (HOMO) energies. We show that excellent results (better than for ionization potentials) can be obtained using standard approximate functionals evaluated on Hartree-Fock or exact-exchange densities for which the extra electron is bound. Although these good results found with limited basis sets are not accidental, we argue that this method cannot be used in general. Thus a positive HOMO indicates that the total energy should not be disregarded, only treated with caution.

引用

页码：2124 / 2129

页数：6

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