Mode-specific chemisorption of CH4 on Pt{110}-(1 × 2) explored by first-principles molecular dynamics

Abstract

The chemisorption of CH4 on Pt{110}-(1 × 2) has been studied by vibrational analysis of the reaction pathway defined by the potential energy surface and, in time reversal, by first-principles molecular dynamics simulations of CH4 associative desorption, with the electronic structure treated explicitly using density functional theory. We find that the symmetric stretch vibration 1 is strongly coupled to the reaction coordinate; our results therefore provide a firm theoretical basis for recently reported state-resolved reactivity measurements, which show that excitation of the 1 normal mode is the most efficient way to enhance the reaction probability. © 2011 American Chemical Society.