Repository: Freie Universität Berlin, Math Department

Examination of the concept of degree of rate control by first-principles kinetic Monte Carlo simulations

Meskine, H. and Matera, S. and Scheffler, M. and Reuter, K. and Metiu, H. (2009) Examination of the concept of degree of rate control by first-principles kinetic Monte Carlo simulations. Surface Science, 603 (10). pp. 1724-1730.



The conceptual idea of degree of rate control (DRC) approaches is to identify the “rate limiting step” in a complex reaction network by evaluating how the overall rate of product formation changes when a small change is made in one of the kinetic parameters. We examine two definitions of this concept by applying it to first-principles kinetic Monte Carlo simulations of the CO oxidation at RuO2(1 1 0). Instead of studying experimental data we examine simulations, because in them we know the surface structure, reaction mechanism, the rate constants, the coverage of the surface and the turn-over frequency at steady-state. We can test whether the insights provided by the DRC are in agreement with the results of the simulations thus avoiding the uncertainties inherent in a comparison with experiment. We find that the information provided by using the DRC is non-trivial: It could not have been obtained from the knowledge of the reaction mechanism and of the magnitude of the rate constants alone. For the simulations the DRC provides furthermore guidance as to which aspects of the reaction mechanism should be treated accurately and which can be studied by less accurate and more efficient methods. We therefore conclude that a sensitivity analysis based on the DRC is a useful tool for understanding the propagation of errors from the electronic structure calculations to the statistical simulations in first-principles kinetic Monte Carlo simulations.

Item Type:Article
Uncontrolled Keywords:Degree of rate control; Microkinetics; First-principles kinetic Monte Carlo; Sensitivity analysis
Subjects:Mathematical and Computer Sciences > Mathematics > Applied Mathematics
Divisions:Department of Mathematics and Computer Science > Institute of Mathematics > Geophysical Fluid Dynamics Group
ID Code:2028
Deposited By: Ulrike Eickers
Deposited On:17 Feb 2017 11:24
Last Modified:03 Mar 2017 14:42

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