Abstract
The dissociation of methane on transition metal surfaces is not only of fundamental interest but also of industrial importance as it represents a rate-controlling step in the steam-reforming reaction used commercially to produce hydrogen. Recently, a specific reaction parameter functional (SRP32-vdW) has been developed, which describes the dissociative chemisorption of CHD(3) at normal incidence on Ni(111), Pt(111), and Pt(211) within chemical accuracy (4.2 kJ/mol). Here, we further test the validity of this functional by comparing the initial sticking coefficients (S(0)), obtained from ab-initio molecular dynamics calculations run using this functional, with those measured with the King and Wells method at different angles of incidence for CHD(3) dissociation on Pt(211). The two sets of data are in good agreement, demonstrating that the SRP32-vdW functional also accurately describes CHD(3) dissociation at off-normal angles of incidence. When the direction of incidence is perpendicular to the step edges, an asymmetry is seen in the reactivity with respect to the surface normal, with S(0) being higher when the molecule is directed toward the (100) step rather than the (111) terrace. Although there is a small shadowing effect, the trends in S(0) can be attributed to different activation barriers for different surface sites, which in turn is related to the generalized co-ordination numbers of the surface atom to which the dissociating molecule is adsorbed in the transition state. Consequently, most reactivity is seen on the least co-ordinated step atoms at all angles of incidence.