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Convenient expression of the rate constant for nonadiabatic transition
Author(s) -
Okuno Yoshishige,
Mashiko Shinro
Publication year - 2004
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.20351
Subject(s) - adiabatic process , reaction rate constant , constant (computer programming) , chemistry , transition rate matrix , adiabatic theorem , transition state , potential energy , partition function (quantum field theory) , quantum , partition (number theory) , product (mathematics) , quantum mechanics , computational chemistry , thermodynamics , physics , kinetics , geometry , mathematics , combinatorics , computer science , programming language , catalysis , biochemistry , statistics
We derived a convenient expression of the rate constant for nonadiabatic transitions, with the intention of making it possible and practical to calculate the rate constant. For this derivation, we first assume that the seam, at which the adiabatic potential energy surfaces of reactant and product electronic states exhibit an avoided crossing, corresponds to the dividing surface of the nonadiabatic transition. Second, we use the probability that a nonadiabatic transition occurs in the seam. Third, the partition function in the seam is described by the local profile of the adiabatic potential energy surfaces of both the reactant and product electronic states. The rate constant expression thus derived not only gives significant insight into understanding nonadiabatic transitions, but also makes it possible to obtain a rough estimate of the rate constant. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005