Mean field treatment of heterogeneous steady state kinetics

[Display omitted] •A new method for solving chemical reaction kinetics with disorder in the rates (unimolecular or bimolecular) is presented.•The method uses a mean-field approximation to quickly compute self-consistent steady state populations.•We illustrate the proposed method with a working examp...

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Veröffentlicht in:Chemical physics letters 2017-10, Vol.685 (C), p.185-190
Hauptverfasser: Geva, Nadav, Vaissier, Valerie, Shepherd, James, Van Voorhis, Troy
Format: Artikel
Sprache:eng
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Zusammenfassung:[Display omitted] •A new method for solving chemical reaction kinetics with disorder in the rates (unimolecular or bimolecular) is presented.•The method uses a mean-field approximation to quickly compute self-consistent steady state populations.•We illustrate the proposed method with a working example of H2 production on a heterogeneous surface. We propose a method to quickly compute steady state populations of species undergoing a set of chemical reactions whose rate constants are heterogeneous. Using an average environment in place of an explicit nearest neighbor configuration, we obtain a set of equations describing a single fluctuating active site in the presence of an averaged bath. We apply this Mean Field Steady State (MFSS) method to a model of H2 production on a disordered surface for which the activation energy for the reaction varies from site to site. The MFSS populations quantitatively reproduce the KMC results across the range of rate parameters considered.
ISSN:0009-2614
1873-4448
DOI:10.1016/j.cplett.2017.07.011