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

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.