1793
Microkinetic Rate Theory:Formalization, Current Limitations, Prospects As Basis for Continuum Rate Theory

Wednesday, 3 October 2018: 09:40
Universal 18 (Expo Center)
M. F. Francis (Brown University)
Microkinetic Rate Theory (MRT) has been an important part of chemical kinetics, being taught in undergraduate physics and chemistry courses, and forming the basis of modern descriptor theory used widely in research. In spite of MRT’s ubiquitous importance, it has remain unformalized and ungeneralized. In this talk, MRT is formalized and generalized. MRT is cast as an algebraic expansion and those matrix elements forming the coefficients of the generalization defined in terms of reaction rate constants, which are in turn connect to statistical mechanics. A transport formulation of MRT is given and it shown that Fickian diffusion is a subset of MRT. MRT is shown to deviate from direct kMC simulations in a certain rate regime which is attributed to phenomenologically distinct stochastic and deterministic rate regimes, similar to diffusion and continuum fluid mechanics, but relevant to chemical and complex kinetics.