Precursor Mediated Microcanonical Trapping Model of Activated Dissociative Chemisorption at Surfaces:Assessment of Dynamical Effects

A precursor mediated microcanonical trapping (PMMT) model of gas-surface reactivity was developed and applied to several benchmark reactions of catalytic interest: i) the dissociative chemisorption and recombinative desorption of hydrogen on Cu(111), ii) the dissociative chemisorption of methane on several transition metal surfaces, and iii) the dissociation of several small alkanes on Pt(111). PMMT model analysis of experiments allowed for determination of transition state properties, which are compared to electronic structure theory (EST) calculations, and allowed for different kinds of experiments to be compared to one another. Dynamical effects were found to be most important for the smallest molecules, but a dynamically-constrained, microcanonical transition state model was found to provide an adequate description of the gas-surface reactivity.