MECHANISM OF GROUND-STATE-FORBIDDEN PHOTOCHEMICAL PERICYCLIC-REACTIONS - EVIDENCE FOR REAL CONICAL INTERSECTIONS

被引：138

作者：

BERNARDI, F ^{[1
]}

DE, S ^{[1
]}

OLIVUCCI, M ^{[1
]}

ROBB, MA ^{[1
]}

机构：

[1] UNIV LONDON KINGS COLL,DEPT CHEM,LONDON WC2R 2LS,ENGLAND

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1990年 / 112卷 / 05期

关键词：

D O I：

10.1021/ja00161a013

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The presence of a conical intersection between the S0 and S1, surfaces for ground-state-forbidden photochemical pericyclic reactions is demonstrated by using results from an effective (valence bond) Hamiltonian and MC-SCF computations. The existence of such topological features is an important feature in the mechanism since it permits a fully efficient return to S0 from the S, excited state. An example is presented for the 2 + 2 cycloaddition reaction of two ethylene molecules and the electrocyclic reaction of cir-butadiene. © 1990, American Chemical Society. All rights reserved.

引用

页码：1737 / 1744

页数：8

共 22 条

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