定域片断轨道基组的对称化

高等学校化学学报 ›› 2003, Vol. 24 ›› Issue (12): 2252.

定域片断轨道基组的对称化

虞忠衡, 徐红, 马艳萍

中国科学院化学研究所分子动态稳态国家重点试验室, 北京 100080

收稿日期:2002-12-25 出版日期:2003-12-24 发布日期:2003-12-24
通讯作者: 虞忠衡(1944年出生),男,博士,研究员,从事物理有机化学研究.E-mail:yuzh@infoc3.icas.ac.cn E-mail:yuzh@infoc3.icas.ac.cn
基金资助:
国家自然科学基金(批准号:20072041,20272063,20032010)资助

Symmetrization of the Localized Fragment Molecular Orbital Basis

YU Zhong-Heng, XU Hong, MA Yan-Ping

State Key Laboratory for Structural Chemistry of Unstable & Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China

Received:2002-12-25 Online:2003-12-24 Published:2003-12-24

摘要/Abstract

摘要： 片断的UHF运算不能保证每个片断轨道具有确切的电子占据数,故Kost定域化是必需的.当片断产生于多键断裂时,在确保目标轨道单占据性的同时,Kost定域破坏了轨道基组的对称性.为此,在Kost定域化后,必须对单占据轨道作2×2对称化旋转后,再作有条件的RHF运算.以乙烯基片断CHCH(波二烯分子中的一个片断)为例,详述了对称化的方法、原理和计算程序.以C-H片断为例,细述三单键片断轨道基组对称化的特殊性.介绍C-HR参考键长选择的判据,探讨键长与选择Gaussian基组大小的关系.

关键词: 片断分子, 片断轨道基组, 轨道基组的对称化, 电子转移

Abstract: The UHFcomputation for a fragment resulted from the breaking of the single bonds can′t ensure that each of the opened-shell delocalized FMO s (fragment molecular orbitals) Ψ_i^ohas a correct electronic occupancy. It is necessary to localize Ψ_i^owith the Kost method. However, the Kost localization destroys the symmetry of the localized FMO basis set Ψ iin the case of fragments such as -CHCH- and CH that are the fragments of polynorbornyl diene and resulted from the breaking of two and three carbon-carbon single bonds respectively. In this work, the localized FMO basis Ψ_ifor ethylenic group was taken as an example, the procedures for symmetrizing Ψ_iare detailed. At a higher Gaussian basis level such as 3-21G, the method that determines the length r of the bond between carbon atom and its one referential hydrogen HR is introduced.

Key words: Fragment molecule, FMO basis set, Symmetriation of the FMO basis set, Electron transfer

中图分类号:

O641

TrendMD:

虞忠衡, 徐红, 马艳萍. 定域片断轨道基组的对称化. 高等学校化学学报, 2003, 24(12): 2252.

YU Zhong-Heng, XU Hong, MA Yan-Ping . Symmetrization of the Localized Fragment Molecular Orbital Basis. Chem. J. Chinese Universities, 2003, 24(12): 2252.

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