Dynamical Study of the Dissociative Chemisorption of CHD(3) on Pd(111)

[Image: see text] The specific reaction parameter (SRP) approach to density functional theory has been shown to model reactions of polyatomic molecules with metal surfaces important for heterogeneous catalysis in the industry with chemical accuracy. However, transferability of the SRP functional among systems in which methane interacts with group 10 metals remains unclear for methane + Pd(111). Therefore, in this work, predictions have been made for the reaction of CHD(3) on Pd(111) using Born–Oppenheimer molecular dynamics while also performing a rough comparison with experimental data for CH(4) + Pd(111) obtained for lower incidence energies. Hopefully, future experiments can test the transferability of the SRP functional among group 10 metals also for Pd(111). We found that the reactivity of CHD(3) on Pd(111) is intermediate between and similar to either Pt(111) or Ni(111), depending on the incidence energy and the initial vibrational state distribution. This is surprising because the barrier height and experiments performed at lower incidence energies than investigated here suggest that the reactivity of Pd(111) should be similar to that of Pt(111) only. The relative decrease in the reactivity of Pd(111) at high incidence energies is attributed to site specificity of the reaction and to dynamical effects such as the bobsled effect and energy transfer from methane to the surface.