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

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.