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ID 17085
file
creator
Kawano, Akio
Saito, Ko
NDC
Chemistry
abstract
We present a microcanonical kinetic theory, which we refer to as the lth-order semi-Markov phase space theory (SMl-PST), for nonadiabatic unimolecular dissociations dominated by standard surface hopping dynamics. In this theory, reaction dynamics is considered as a stochastic transport, which is described as an lth-order Markov chain, among cells produced from partition of the available phase space. Kinetic equations are derived by importing residence time of stay cells as a random variable into the Markov chain. An efficient method to determine the parameters of the kinetic equations is developed, which is made up of Monte Carlo phase space integration and short-time trajectory calculations. As a test calculation, the SMl-PST has been applied to a model system for the predissociation of collinear N2O. We show that the SMl-PST works well, giving rate coefficients of much better accuracy than conventional statistical theory and of comparable accuracy to standard trajectory calculations with a lower computational effort.
journal title
Journal of Chemical Physics
volume
Volume 116
issue
Issue 20
start page
8660
end page
8676
date of issued
2002-05-22
publisher
American Institute of Physics
issn
0021-9606
ncid
publisher doi
language
eng
nii type
Journal Article
HU type
Journal Articles
DCMI type
text
format
application/pdf
text version
publisher
rights
Copyright (c) 2002 American Institute of Physics.
relation url
department
Graduate School of Science