Hybrid exchange-correlation functional for core, valence, and Rydberg excitations: core-valence-Rydberg B3LYP.
Hybrid exchange-correlation functional for core, valence, and Rydberg excitations: core-valence-Rydberg B3LYP.
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DOI：
10.1063/1.2227379
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发表时间：
2006-08
期刊：
影响因子：
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通讯作者：
A. Nakata;Y. Imamura;H. Nakai
中科院分区：
文献类型：
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作者：
A. Nakata;Y. Imamura;H. Nakai
提出了核价Rydberg-Becke三参数交换（B3）+Lee-Yang-Parr（LYP）关联泛函（CVR-B3 LYP），改进了对核价B3 LYP（CV-B3 LYP）Rydberg-Becke激发的描述. CV-B3 LYP以高精度描述了从核心和占据价轨道到未占据价轨道的激发，但未能描述到Rydberg轨道的激发。CVR-B3 LYP在未占据价态和Rydberg区分别采用适当的Hartree-Fock交换，克服了CV-B3 LYP的缺点。数值评估证实，含时密度泛函理论计算CVR-B3 LYP成功地描述不仅核心激发，但也里德堡激发具有合理的精度。
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.