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 firstprinciples kinetic Monte Carlo simulations. Surface Science, 603 (10). pp. 17241730.

PDF
481kB 
Abstract
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 firstprinciples 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 turnover frequency at steadystate. 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 nontrivial: 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 firstprinciples kinetic Monte Carlo simulations.
Item Type:  Article 

Uncontrolled Keywords:  Degree of rate control; Microkinetics; Firstprinciples 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 
Repository Staff Only: item control page