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Stochastic simulation of catalytic surface reactions in the fast diffusion limit

Mastny, Ethan A. and Haseltine, Eric L. and Rawlings, James B. (2006) Stochastic simulation of catalytic surface reactions in the fast diffusion limit. Journal of Chemical Physics, 125 (19). Art. No. 194715. ISSN 0021-9606. doi:10.1063/1.2390696.

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The master equation of a lattice gas reaction tracks the probability of visiting all spatial configurations. The large number of unique spatial configurations on a lattice renders master equation simulations infeasible for even small lattices. In this work, a reduced master equation is derived for the probability distribution of the coverages in the infinite diffusion limit. This derivation justifies the widely used assumption that the adlayer is in equilibrium for the current coverages and temperature when all reactants are highly mobile. Given the reduced master equation, two novel and efficient simulation methods of lattice gas reactions in the infinite diffusion limit are derived. The first method involves solving the reduced master equation directly for small lattices, which is intractable in configuration space. The second method involves reducing the master equation further in the large lattice limit to a set of differential equations that tracks only the species coverages. Solution of the reduced master equation and differential equations requires information that can be obtained through short, diffusion-only kinetic Monte Carlo simulation runs at each coverage. These simulations need to be run only once because the data can be stored and used for simulations with any set of kinetic parameters, gas-phase concentrations, and initial conditions. An idealized CO oxidation reaction mechanism with strong lateral interactions is used as an example system for demonstrating the reduced master equation and deterministic simulation techniques.

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Additional Information:©2006 American Institute of Physics (Received 13 June 2006; accepted 13 October 2006; published online 21 November 2006) This material is based upon work supported under a National Science Foundation Graduate Research Fellowship. The authors would like to thank Professor Yannis Kevrekidis and Professor Manos Mavrikakis for helpful discussions of aspects of this paper.
Subject Keywords:carbon compounds; surface chemistry; catalysis; oxidation; reaction kinetics theory; stochastic processes; adsorbed layers; diffusion; master equation; probability; Monte Carlo methods
Issue or Number:19
Record Number:CaltechAUTHORS:MASjcp06
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:6421
Deposited By: Archive Administrator
Deposited On:08 Dec 2006
Last Modified:08 Nov 2021 20:33

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