长程校正混合密度泛函的系统优化

Systematic optimization of long-range corrected hybrid density functionals.

作者信息

Chai Jeng-Da, Head-Gordon Martin

机构信息

Department of Chemistry, University of California and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.

出版信息

J Chem Phys. 2008 Feb 28;128(8):084106. doi: 10.1063/1.2834918.

DOI:10.1063/1.2834918

PMID:18315032

Abstract

A general scheme for systematically modeling long-range corrected (LC) hybrid density functionals is proposed. Our resulting two LC hybrid functionals are shown to be accurate in thermochemistry, kinetics, and noncovalent interactions, when compared with common hybrid density functionals. The qualitative failures of the commonly used hybrid density functionals in some "difficult problems," such as dissociation of symmetric radical cations and long-range charge-transfer excitations, are significantly reduced by the present LC hybrid density functionals.

摘要

提出了一种用于长程校正（LC）杂化密度泛函系统建模的通用方案。与常见的杂化密度泛函相比，我们得到的两种LC杂化泛函在热化学、动力学和非共价相互作用方面表现出准确性。在一些“难题”中，如对称自由基阳离子的解离和长程电荷转移激发，常用杂化密度泛函的定性失败被目前的LC杂化密度泛函显著减少。