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

TL;DR

This study evaluates the concept of degree of rate control (DRC) using first-principles kinetic Monte Carlo simulations of CO oxidation on RuO2(110), demonstrating its usefulness in identifying key reaction steps and guiding modeling accuracy.

Contribution

The paper applies and tests two definitions of DRC within first-principles kinetic Monte Carlo simulations, providing insights into reaction mechanisms and modeling accuracy.

Findings

DRC offers non-trivial insights beyond reaction mechanism and rate constants.

DRC guides which reaction steps require high-accuracy modeling.

Sensitivity analysis with DRC helps propagate electronic structure errors in simulations.

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 first-principles kinetic Monte Carlo simulations of the CO oxidation at RuO2(110). 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.