The role of steps in the dissociation of H(2) on Mg(0001).

The role of steps in the dissociation of molecules on metal surfaces has been extensively investigated in the past. In particular, both theoretical calculations and experimental results for H(2) dissociation on transition metal (TM) surfaces show that steps can significantly increase the reactivity, leading to higher metal-H binding energies and lower activation energies. Here we have used density functional theory (DFT) with the generalized gradient approximation (GGA) to investigate the role of steps on the Mg(0001) surface in the dissociation of H(2) and the binding of H to the metal surface. Our results follow those found for TM surfaces as far as H adsorption energies are concerned, namely that adsorption energies are higher near the steps. However, we find that the activation energy for the dissociation of hydrogen is hardly affected by the presence of steps, with a DFT-GGA value of 0.85 eV, only marginally lower than the value 0.87 eV found on the flat Mg(0001) surface.