Potential energy surface and dissociative cleavage of chlorobenzene radical anion

被引：32

作者：

Beregovaya, IV ^{[1
]}

Shchegoleva, LN ^{[1
]}

机构：

[1] Russian Acad Sci, Siberian Branch, Novosibirsk Organ Chem Inst, Novosibirsk 630090, Russia

来源：

CHEMICAL PHYSICS LETTERS | 2001年 / 348卷 / 5-6期

基金：

俄罗斯基础研究基金会;

关键词：

D O I：

10.1016/S0009-2614(01)01171-X

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：

Potential energy surface (PES) of the short-lived PhCl- radical anion has been studied by ROHF/6-31+G* and MP2/6-31+G*//ROHF/6-31+G* calculations. The PES peculiarities were found to result from two reasons: (a) the quasi-degeneracy of PhCl- pi states; (b) the presence of a low-lying repulsive sigma term. The anion meta-stable (2)Pi state has been located, and transition state for C-Cl cleavage has been found revealing an asymmetrical non-planar structure. Possible mechanisms of halobenzene anions dissociative cleavage are discussed, with the PhCl- as a model. (C) 2001 Elsevier Science B.V. All rights reserved.

引用

页码：501 / 506

页数：6

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