A two-dimensional Born-Oppenheimer treatment of intramolecular electron transfer reactions

被引：9

作者：

Basilevsky, MV

Rostov, IV

Newton, MD

机构：

[1] Karpov Inst Phys Chem, Moscow 103064, Russia

[2] Brookhaven Natl Lab, Dept Chem, Upton, NY 11973 USA

来源：

JOURNAL OF ELECTROANALYTICAL CHEMISTRY | 1998年 / 450卷 / 01期

基金：

俄罗斯基础研究基金会;

关键词：

D O I：

10.1016/S0022-0728(97)00619-0

中图分类号：

O65 [分析化学];

学科分类号：

070302 ; 081704 ;

摘要：

The Born-Oppenheimer (BO) formulation of polar solvation is developed and implemented at the semiemperical (PM3) configuration interaction (CI) level, yielding estimates of electron transfer (ET) coupling elements (V-0) for intramolecular ET in several families of radical ion systems. In contrast to the traditional treatment based on a single solvent coordinate and a fixed gas-phase coupling element, the present treatment yields a self-consistent characterization of kinetic parameters in a 2-dimensional solvent framework which includes an exchange coordinate. The dependence of V-0 on inertial solvent contributions and on donor/acceptor separation (r(DA)) is discussed. (C) 1998 Elsevier Science S.A. All rights reserved.

引用

页码：69 / 82

页数：14

共 33 条

[1] APPLICATION OF GENERALIZED TRANSITION-STATE THEORY FOR CALCULATION OF THE RATE-CONSTANT OF A CHEMICAL-REACTION WITH CHARGE-TRANSFER IN A POLAR-SOLVENT [J].