CORRESPONDENCE OF CANONICAL AND MICROCANONICAL RATE CONSTANTS USING VARIATIONAL TRANSITION-STATE THEORY FOR SIMPLE BOND FISSIONS

被引：36
|
作者：
SCHRANZ, HW
RAFF, LM
THOMPSON, DL
机构：
[1] Department of Chemistry, Oklahoma State University, Stillwater
来源：
CHEMICAL PHYSICS LETTERS | 1990年 / 171卷 / 1-2期
关键词：
D O I：
10.1016/0009-2614(90)80052-F
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：
The different evaluation of microcanonical and canonical variational transition state rate constants by Markov sampling techniques is discussed. It is well known that, in the evaluation of canonical rate constants, sampling the full phase space of the system is unnecessary and that an equivalent and far more efficient procedure is to perform a Markov walk over configuration space. It is shown that an analogous improvement in efficiency is possible in the case of microcanonical rate constants. The close relationship of canonical and microcanonical averages is observed. © 1990.
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页码：68 / 76
页数：9
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