On the dissociation of aromatic radical anions in solution

被引：46

作者：

Laage, D

Burghardt, I

Sommerfeld, T

Hynes, JT

机构：

[1] Ecole Normale Super, CNRS UMR 8460, PASTEUR, Dept Chim, F-75231 Paris 05, France

[2] Ecole Normale Super, CNRS UMR 8642, Dept Chim, F-75231 Paris 05, France

[3] Heidelberg Univ, Inst Phys Chem, D-69120 Heidelberg, Germany

[4] Univ Colorado, Dept Chem & Biochem, Boulder, CO 80309 USA

来源：

CHEMPHYSCHEM | 2003年 / 4卷 / 01期

关键词：

D O I：

10.1002/cphc.200390009

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：

A new theoretical formulation is given for the reaction rate and path for the important reaction class of aromatic radical anion dissociation in solution [Ar-X](-.)-->Ar-. + X-, and is illustrated for the case of the cyanochlorobenzene radical anion [CN-Phi-Cl](-.) in dimethylformamide. Among the theory's novel features is the inclusion of the conical intersection aspect of this ground electronic state problem, which is key in allowing the reaction to occur and which has a significant impact on the reaction barrier height. Reasonable agreement with the experimental rate is found.

引用

页码：61 / 66

页数：6

共 59 条

[41] IONIZATION-POTENTIALS AND ELECTRON-AFFINITIES IN AQUEOUS-SOLUTION [J].