用于内层、价层和里德堡激发的杂化交换关联泛函：内层-价层-里德堡B3LYP

Hybrid exchange-correlation functional for core, valence, and Rydberg excitations: core-valence-Rydberg B3LYP.

作者信息

Nakata Ayako, Imamura Yutaka, Nakai Hiromi

机构信息

Department of Chemistry, School of Science and Engineering, Waseda University, Tokyo 169-8555, Japan.

出版信息

J Chem Phys. 2006 Aug 14;125(6):64109. doi: 10.1063/1.2227379.

DOI:10.1063/1.2227379

PMID:16942275

Abstract

The core-valence-Rydberg Becke's three-parameter exchange (B3)+Lee-Yang-Parr (LYP) correlation functional (CVR-B3LYP) is proposed as a means to improve descriptions of Rydberg excitations of core-valence B3LYP (CV-B3LYP). CV-B3LYP describes excitations from both core and occupied valence orbitals to unoccupied valence orbitals with high accuracy but fails to describe those to Rydberg orbitals. CVR-B3LYP, which adopts the appropriate portions of Hartree-Fock exchange for unoccupied valence and Rydberg regions separately, overcomes the disadvantage of CV-B3LYP. Numerical assessment confirms that time-dependent density functional theory calculations with CVR-B3LYP succeed in describing not only core excitations but also Rydberg excitations with reasonable accuracy.

摘要

提出了核心价层里德堡贝克三参数交换（B3）+李-杨-帕尔（LYP）相关泛函（CVR-B3LYP），作为改进核心价层B3LYP（CV-B3LYP）里德堡激发描述的一种方法。CV-B3LYP能高精度地描述从核心轨道和占据的价层轨道到未占据价层轨道的激发，但无法描述到里德堡轨道的激发。CVR-B3LYP分别对未占据价层区域和里德堡区域采用了哈特里-福克交换的适当部分，克服了CV-B3LYP的缺点。数值评估证实，使用CVR-B3LYP进行含时密度泛函理论计算不仅能成功地以合理精度描述核心激发，还能描述里德堡激发。