Thermal Rates and High-Temperature Tunneling from Surface Reaction Dynamics and First-Principles

Studying dynamics of the dissociative adsorption and recombinative desorption of hydrogen on copper surfaces has shaped our atomic-scale understanding of surface chemistry, yet experimentally determining the thermal rates for these processes, which dictate the outcome of catalytic reactions, has been impossible so far. In this work, we determine the thermal rate constants for dissociative adsorption and recombinative desorption of hydrogen on Cu(111) between 200 and 1000 K using data from reaction dynamics experiments. Contrary to current understanding, our findings demonstrate the predominant role of quantum tunneling, even at temperatures as high as 400 K. We also provide precise values for the reaction barrier (0.619 ± 0.020 eV) and adsorption energy (0.348 ± 0.026 eV) for H₂ on Cu(111). Remarkably, the thermal rate constants are in excellent agreement with a first-principles quantum rate theory based on a new implementation of ring polymer molecular dynamics for reactions on surfaces, paving the way to discovering better catalysts using reliable and efficient computational methods.