Nonthermalized Precursor-Mediated Dissociative Chemisorption at High Catalysis Temperatures

Quasiclassical trajectory calculations and vibrational-state-selected beam-surface measurements of CH₄ chemisorption on Ir(111) reveal a nonthermal, hot-molecule mechanism for C-H bond activation. Low-energy vibrationally excited molecules become trapped in the physisorption well and react before vibrational and translational energies accommodate the surface. The reaction probability is strongly surface-temperature-dependent and arises from the pivotal role of Ir atom thermal motion. In reactive trajectories, the mean outward Ir atom displacement largely exceeds that of the transition-state geometry obtained through a full geometry optimization. The study also highlights a new way for (temporary) surface defects to impact high-temperature heterogeneous catalytic reactivity. Instead of reactants diffusing to and competing for geometrically localized lower barrier sites, transient, thermally activated surface atom displacements deliver low-barrier surface reaction geometries to the physisorbed reactants.