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Thermal reaction rates with a two‐point flux–flux correlation function
Author(s) -
Lefebvre R.,
Moiseyev N.,
Ryaboy V.
Publication year - 1994
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.560510613
Subject(s) - flux (metallurgy) , flexibility (engineering) , chemistry , representation (politics) , limit (mathematics) , function (biology) , thermodynamics , heat flux , thermal , reaction rate constant , correlation function (quantum field theory) , physics , mathematical analysis , mathematics , classical mechanics , quantum mechanics , kinetics , statistics , heat transfer , organic chemistry , evolutionary biology , politics , political science , dielectric , law , biology
The thermal rate constant of a bimolecular reaction is shown to be expressible as the time limit of the time integral of a correlation function involving the reactive flux at two different points along the path leading from reactants to products. This extension provides some additional flexibility in the finite basis‐set representation of the rate given by Miller–Schwartz–Tromp [J. Chem. Phys. 79 , 4889 (1983)]. Some of the features of this expression are examined in the case of one‐dimensional Eckart barrier. © 1994 John Wiley & Sons, Inc.