VARIATIONAL TRANSITION-STATE THEORY FOR MULTIDIMENSIONAL ACTIVATED RATE-PROCESSES IN THE PRESENCE OF ANISOTROPIC FRICTION

被引：32

作者：

BEREZHKOVSKII, AM ^{[1
]}

FRISHMAN, AM ^{[1
]}

POLLAK, E ^{[1
]}

机构：

[1] LY KARPOV PHYS CHEM RES INST,MOSCOW 103064,RUSSIA

来源：

JOURNAL OF CHEMICAL PHYSICS | 1994年 / 101卷 / 06期

关键词：

D O I：

10.1063/1.467400

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：

Variational transition state theory (VTST) is applied to the study of the activated escape of a particle trapped in a multidimensional potential well and coupled to a heat bath. Special attention is given to the dependence of the rate constant on the friction coefficients in the case of anisotropic friction. It is demonstrated explicitly that both the traditional as well as the nontraditional scenarios for the particle escape are recovered uniformly within the framework of VTST. Effects such as saddle point avoidance and friction dependence of the activation energy are derived from VTST using optimized planar dividing surfaces.

引用

页码：4778 / 4789

页数：12

共 52 条

[1] TRANSIENT KINETICS OF CHEMICAL-REACTIONS WITH BOUNDED DIFFUSION PERPENDICULAR TO THE REACTION COORDINATE - INTRAMOLECULAR PROCESSES WITH SLOW CONFORMATIONAL-CHANGES [J].