A Lattice Kinetic Monte Carlo Solver for First-Principles Microkinetic Trend Studies

• Published in: Journal of chemical theory and computation Vol. 14; no. 3; pp. 1583 - 1593
• Main Authors: Hoffmann, Max J, Bligaard, Thomas
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 13.03.2018
• Subjects: Adsorbates; Chemical reactions; Computer simulation; Diffusion rate; First principles; Fruit flies; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Mathematical models; MATHEMATICS AND COMPUTING; Monte Carlo simulation; Oxidation; Rate constants
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.7b00683

Mean-field microkinetic models in combination with Brønsted–Evans–Polanyi like scaling relations have proven highly successful in identifying catalyst materials with good or promising reactivity and selectivity. Analysis of the microkinetic model by means of lattice kinetic Monte Carlo promises a faithful description of a range of atomistic features involving short-range ordering of species in the vicinity of an active site. In this paper, we use the “fruit fly” example reaction of CO oxidation on fcc(111) transition and coinage metals to motivate and develop a lattice kinetic Monte Carlo solver suitable for the numerically challenging case of vastly disparate rate constants. As a result, we show that for the case of infinitely fast diffusion and absence of adsorbate-adsorbate interaction it is, in fact, possible to match the prediction of the mean-field-theory method and the lattice kinetic Monte Carlo method. As a corollary, we conclude that lattice kinetic Monte Carlo simulations of surface chemical reactions are most likely to provide additional insight over mean-field simulations if diffusion limitations or adsorbate–adsorbate interactions have a significant influence on the mixing of the adsorbates.