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An analysis of the rate of isomerization in molecules with an asymmetric double well potential
Author(s) -
Zhao Meishan
Publication year - 1993
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.19930110603
Subject(s) - isomerization , chemistry , statistical physics , relaxation (psychology) , trajectory , computational chemistry , quantum mechanics , physics , catalysis , psychology , social psychology , biochemistry
The classical theory of the rate of unimolecular isomerization developed by Gray and Rice as extended by Zhao and Rice is applied to the calculation of the rate of isomerization in model systems which have linear asymmetric double well potentials. We are interested in this system for two reasons. First, we are interested in the detailed dynamical processes for the mentioned system because it is widely related to practical chemical reactions. Second, the present model system has an asymmetric double well potential, which provides a different test of the accuracy of the approximations used in the Gray‐Zhao‐Rice theory than posed by previous applications. We have calculated relaxation rates and relaxation times for the model systems on different time scales. We find that for the systems under studies the Gray‐Zhao‐Rice version of the classical theory of isomerization rate yields values in good agreement with those generated from trajectory calculations and from the Reactive Island theory of De Leon et al.