Premium
The stochastic theory and its relations to the general reaction rate theory
Author(s) -
Christov S. G.
Publication year - 1989
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.560360321
Subject(s) - transition state theory , statistical physics , viscosity , quantum , quantum tunnelling , thermodynamics , physics , mathematics , quantum mechanics , kinetics , reaction rate constant
A short review of the recent development of the stochastic approach to chemical reactions in condensed media is made. The relations of this approach to a general formulation of chemical kinetics are discussed on the basis of a many‐frequency oscillator model. It is shown that the classical transition‐state theory is not a particular case of the stochastic theory neither in the case of small viscosity nor in the case of large viscosity. The recent quantum generalizations of the stochastic theory are identical to earlier results of a quantum transition‐state theory that correspond to the case of large viscosity. Such generalizations based on previous results of a collision theory are made for the case of small viscosity. It is shown that these quantum generalizations of the stochastic theory are possible only in the temperature range of moderate tunneling defined in terms of a characteristic temperature.