Test of the Transferability of the Specific Reaction Parameter Functional for H(2) + Cu(111) to D(2) + Ag(111)

[Image: see text] The accurate description of the dissociative chemisorption of a molecule on a metal surface requires a chemically accurate description of the molecule–surface interaction. Previously, it was shown that the specific reaction parameter approach to density functional theory (SRP–DFT) enables accurate descriptions of the reaction of dihydrogen with metal surfaces in, for instance, H(2) + Pt(111), H(2) + Cu(111), and H(2) + Cu(100). SRP–DFT likewise allowed a chemically accurate description of dissociation of methane on Ni(111) and Pt(111), and the SRP functional for CH(4) + Ni(111) was transferable to CH(4) + Pt(111), where Ni and Pt belong to the same group. Here, we investigate whether the SRP density functional derived for H(2) + Cu(111) also gives chemically accurate results for H(2) + Ag(111), where Ag belongs to the same group as Cu. To do this, we have performed quasi-classical trajectory calculations using the six-dimensional potential energy surface of H(2) + Ag(111) within the Born–Oppenheimer static surface approximation. The computed reaction probabilities are compared with both state-resolved associative desorption and molecular beam sticking experiments. Our results do not yet show transferability, as the computed sticking probabilities and initial-state selected reaction probabilities are shifted relative to experiment to higher energies by about 2–3 kcal/mol. The lack of transferability may be due to the different character of the SRP functionals for H(2) + Cu and CH(4) + group 10 metals, the latter containing a van der Waals correlation functional and the former not.