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The dynamic and the stochastic reaction rate approaches to nonradiative processes in condensed media
Author(s) -
Christov S. G.
Publication year - 1992
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560440102
Subject(s) - harmonic oscillator , transition state theory , equivalence (formal languages) , statistical physics , basis (linear algebra) , stochastic process , mathematics , thermodynamics , physics , quantum mechanics , reaction rate constant , kinetics , pure mathematics , statistics , geometry
Abstract A comparison is made between the exact classical dynamic theory and the stochastic theory of reaction rates in dense media. The conditions of their equivalence are derived on the basis of a harmonic oscillator model. It is shown in a direct way that in the general case of a multidimensional system the approximate activated complex (transition‐state) theory is not identical to the stochastic theory at any value of the viscosity coefficient. © 1992 John Wiley & Sons, Inc.