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Reformulation and Solution of the Master Equation for Multiple-Well Chemical Reactions
Ist Teil von
The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 2013-11, Vol.117 (46), p.12146-12154
Ort / Verlag
Washington, DC: American Chemical Society
Erscheinungsjahr
2013
Link zum Volltext
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
We consider an alternative formulation of the master equation for complex-forming chemical reactions with multiple wells and bimolecular products. Within this formulation the dynamical phase space consists of only the microscopic populations of the various isomers making up the reactive complex, while the bimolecular reactants and products are treated equally as sources and sinks. This reformulation yields compact expressions for the phenomenological rate coefficients describing all chemical processes, i.e., internal isomerization reactions, bimolecular-to-bimolecular reactions, isomer-to-bimolecular reactions, and bimolecular-to-isomer reactions. The applicability of the detailed balance condition is discussed and confirmed. We also consider the situation where some of the chemical eigenvalues approach the energy relaxation time scale and show how to modify the phenomenological rate coefficients so that they retain their validity.