KINETICS OF CHEMICAL-REACTIONS IN CONDENSED MEDIA IN THE FRAMEWORK OF THE 2-DIMENSIONAL STOCHASTIC-MODEL

被引:30
作者
BASILEVSKY, MV
RYABOY, VM
WEINBERG, NN
机构
[1] Karpov Institute of Physical Chemistry, 103064 Moscow K-64
关键词
D O I
10.1021/j100387a020
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 chemical reaction proceeding in a continuum medium is modeled as a pair of stochastic equations with a δ-correlated random force. A numerical method for calculating the rate constant is elaborated in a quasi-one-dimensional approximation. Exact rate constants are found over a wide range of characteristic system parameters. The existence of a significant region with a nonequilibrium kinetic behavior, as predicted previously by Berezhkovskii and Zitserman, is confirmed. Moreover, the nonequilibrium rate constant is shown to describe not only the extreme of quasi-one-dimensional dynamics but also the case when the complete two-dimensional equation of motion operates. © 1990 American Chemical Society.
引用
收藏
页码:8734 / 8740
页数:7
相关论文
共 19 条
[1]   TRANSIENT KINETICS OF CHEMICAL-REACTIONS WITH BOUNDED DIFFUSION PERPENDICULAR TO THE REACTION COORDINATE - INTRAMOLECULAR PROCESSES WITH SLOW CONFORMATIONAL-CHANGES [J].
AGMON, N ;
HOPFIELD, JJ .
JOURNAL OF CHEMICAL PHYSICS, 1983, 78 (11) :6947-6959
[2]   TUNNELLING IN A DOUBLE-WELL SYSTEM WITH ALLOWANCE MADE FOR THE RELAXATION [J].
BASILEVSKY, MV ;
RYABOY, VM .
MOLECULAR PHYSICS, 1981, 44 (04) :785-798
[3]   DECAY DYNAMICS OF TRIATOMIC-MOLECULES - QUANTUM CALCULATIONS FOR NON-SYMMETRIC LINEAR-SYSTEMS [J].
BASILEVSKY, MV ;
RYABOY, VM .
CHEMICAL PHYSICS, 1984, 86 (1-2) :67-83
[4]  
BASILEVSKY MV, IN PRESS CHEM PHYS
[5]   ANOMALOUS REGIME FOR DECAY OF THE METASTABLE STATE - AN EXTENSION OF MULTIDIMENSIONAL KRAMERS THEORY [J].
BEREZHKOVSKII, AM ;
ZITSERMAN, VY .
CHEMICAL PHYSICS LETTERS, 1989, 158 (05) :369-374
[6]  
BEREZHKOVSKII AM, IN PRESS PHYS A
[7]   ADIABATIC ELECTRON-TRANSFER IN POLAR MEDIA - QUANTUM TRANSITION-STATE THEORY [J].
DAKHNOVSKII, YI ;
OVCHINNIKOV, AA .
MOLECULAR PHYSICS, 1986, 58 (02) :237-252
[8]   CROSSOVER FROM THERMAL HOPPING TO QUANTUM TUNNELING [J].
GRABERT, H ;
WEISS, U .
PHYSICAL REVIEW LETTERS, 1984, 53 (19) :1787-1790
[9]   THE STABLE STATES PICTURE OF CHEMICAL-REACTIONS .2. RATE CONSTANTS FOR CONDENSED AND GAS-PHASE REACTION MODELS [J].
GROTE, RF ;
HYNES, JT .
JOURNAL OF CHEMICAL PHYSICS, 1980, 73 (06) :2715-2732
[10]   ESCAPE FROM A METASTABLE STATE [J].
HANGGI, P .
JOURNAL OF STATISTICAL PHYSICS, 1986, 42 (1-2) :105-148