First-principles full-dimensional modelling of vibrational energy transfer of molecule scattering from metal surfaces

Energy transfer during molecular collisions on metal surfaces plays a pivotal role in a host of critical interfacial processes. Despite significant efforts, our understanding of relevant energy transfer mechanisms, even in an extensively-studied benchmark like NO scattering from Au(111), remains far from complete. To fully disentangle different energy transfer channels, we develop a first-principles nonadiabatic dynamical model that incorporates explicitly all degrees of freedom and the interfacial electron transfer. Our simulations successfully reproduce most experimental observations on vibrational relaxation and excitation of NO molecules under varying initial conditions. The observed steric effect varying with the initial vibrational state is understood by the change of orientational dependence of the metal-to-molecule electron transfer. This model also identifies that translational motion could couple to molecular vibration directly, while the translation-to-electron nonadiabatic coupling is not significant. These valuable insights highlight the importance of treating both adiabatic and nonadiabatic energy transfer pathways on equal footing, offering significant implications for modeling energy transfer processes in more complex systems, such as plasmonic photocatalysis.