Designing new SRP density functionals including non-local vdW-DF2 correlation for H2 + Cu(111) and their transferability to H2 + Ag(111), Au(111) and Pt(111)

Abstract

Specific reaction parameter density functionals (SRP-DFs) that can describe dissociative chemisorption molecular beam experiments of hydrogen (H₂) on cold transition metal surfaces with chemical accuracy have so far been shown to be only transferable among different facets of the same metal, but not among different metals. We design new SRP-DFs that include non-local vdW-DF2 correlation for the H₂ + Cu(111) system, and evaluate their transferability to the highly activated H₂ + Ag(111) and H₂ + Au(111) systems and the non-activated H₂ + Pt(111) system. We design our functionals for the H₂ + Cu(111) system since it is the best studied system both theoretically and experimentally. Here we demonstrate that a SRP-DF fitted to reproduce molecular beam sticking experiments for H₂ + Cu(111) with chemical accuracy can also describe such experiments for H₂ + Pt(111) with chemical accuracy, and vice versa. Chemically accurate functionals have been obtained that perform very well with respect to reported van der Waals well geometries, and which improve the description of the metal over current generalized gradient approximation (GGA) based SRP-DFs. From a systematic comparison of our new SRP-DFs that include non-local correlation to previously developed SRP-DFs, for both activated and non-activated systems, we identify non-local correlation as a key ingredient in the construction of transferable SRP-DFs for H₂ interacting with transition metals. Our results are in excellent agreement with experiment when accurately measured observables are available. It is however clear from our analysis that, except for the H₂ + Cu(111) system, there is a need for more, more varied, and more accurately described experiments in order to further improve the design of SRP-DFs. Additionally, we confirm that, when including non-local correlation, the sticking of H₂ on Cu(111) is still well described quasi-classically.