Best-of-Both-Worlds Predictive Approach to Dissociative Chemisorption on Metals

Predictive capability, accuracy, and affordability are essential features of a theory that is capable of describing dissociative chemisorption on a metal surface. This type of reaction is important for heterogeneous catalysis. Here we present an approach in which we use diffusion Monte Carlo (DMC) to pin the minimum barrier height and construct a density functional that reproduces this value. This predictive approach allows the construction of a potential energy surface at the cost of density functional theory while retaining near DMC accuracy. Scrutinizing effects of energy dissipation and quantum tunneling, dynamics calculations suggest the approach to be of near chemical accuracy, reproducing molecular beam sticking experiments for the showcase H₂ + Al(110) system to ∼1.4 kcal/mol.