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On the Theory of Rate Processes in Condensed Media
Author(s) -
Fain V. M.
Publication year - 1974
Publication title -
physica status solidi (b)
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.51
H-Index - 109
eISSN - 1521-3951
pISSN - 0370-1972
DOI - 10.1002/pssb.2220630142
Subject(s) - adiabatic process , adiabatic theorem , reaction rate constant , character (mathematics) , transition rate matrix , electron , constant (computer programming) , chemistry , harmonic , transition state , chemical bond , physics , statistical physics , quantum mechanics , mathematics , kinetics , statistics , geometry , computer science , programming language , biochemistry , catalysis
A general theory of electronic transitions in condensed media is developed which describes in particular various possible chemical reactions in condensed media. The approximations used are: the Born‐Oppenheimer adiabatic approximation, the Condon approximation to describe the dependence of the matrix elements of the electron transition, and the harmonic approximation to describe the nuclear motion in the initial and final electronic states. In the framework of these approximations general expressions are obtained for the rate constants of the corresponding reactions. In a certain approximation these constants can be reduced to the form given by the Eyring theory of rate processes. In the other region the expressions for the rate constants are obtained which are of an essentially different character and are interpreted in terms of the theory of the multiphonon transitions. Reactions are considered which occur only with a conformation transition of the system as well as those which are accompanied by conformation transitions and by breaking of a chemical bond.