title: The importance of tunneling in the first hydrogenation step in ammonia synthesis over a Ru(0001) surface.
abstract: The hydrogenation of nitrogen (N(ads)+H(ads)-->NH(ads)) on metal surfaces is an important step in ammonia catalysis. We investigate the reaction dynamics of this hydrogenation step by time independent scattering theory and variational transition state theory (VTST) including tunneling corrections. The potential energy surface is derived by hybrid density functional theory on a model cluster composed of 12 ruthenium atoms resembling a Ru(0001) surface. The scattering calculations are performed on a reduced dimensionality potential energy hypersurface, where two dimensions are treated explicitly and all others are included implicitly by the zero-point correction. The VTST calculations include quantum effects along the reaction coordinate by applying the small curvature tunneling scheme. Even at room temperature (where ruthenium already shows catalytic activity) we find rate enhancement by tunneling by a factor of approximately 70. Inspection of the reaction probabilities shows that the major contribution to reactivity comes from the vibrational ground state of the reactants into vibrationally excited product states. The reaction rates are higher than determined in previous studies, and are compatible with experimental overall rates for ammonia synthesis.
authors.affiliation: Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3HQ, United Kingdom. Christofer.Tautermann@chem.ox.ac.uk
authors.forename: Christofer S
authors.initials: CS
authors.lastname: Tautermann
authors.forename: David C
authors.initials: DC
authors.lastname: Clary