Dissociation of CHD3 on Cu(111), Cu(211), and single atom alloys of Cu(111).

In order to model accurately reactions of polyatomic molecules with metal surfaces important for heterogeneous catalysis in industry, the Specific Reaction Parameter (SRP) approach to density functional theory has been developed. This approach has been shown to describe the dissociation of CHD3 on Ni(111), Pt(111), and Pt(211) with chemical accuracy. In this work, predictions have been made for the reaction of CHD3 on Cu(111) and Cu(211) using barriers, elbow plots, and ab initio molecular dynamics. Future experiments could hopefully prove the transferability of the SRP functional to systems in which methane reacts with flat and stepped surfaces of adjacent groups of the periodic table, by comparison with our predictions. Moreover, the effect of a so-called single atom alloy on the reactivity of methane is investigated by making predictions for CHD3 on Pt-Cu(111) and Pd-Cu(111). It is found that the reactivity is only increased for Pt-Cu(111) near the alloyed atom, which is not only caused by the lowering of the barrier height but also by changes in the dynamical pathway and reduction of energy transfer from methane to the surface.