Effects of coverage on the structures, energetics, and electronics of oxygen adsorption on RuO2(110)

Plane-wave supercell DFT calculations within the PW91 generalized gradient approximation are used to examine the influence of oxygen coverage on the structure, energetics, and electronics of the RuO2(110) surface. Filling of O(br) and O(cus) sites is exothermic with respect to molecular O2 at all coverages and causes changes in local Ru electronic structure consistent with the changing metal coordination. By fitting the surface energies of a large number of surface configurations to a two-body interaction model, an O atom is calculated to be bound by 2.55 eV within a filled O(br) row and by 0.98 eV along an otherwise vacant O(cus) row. Lateral interactions modify these binding energies by up to 20%. O(cus)-O(cus) interactions are repulsive and diminish binding energy with increasing O(cus) filling. Due to the favorable relief of local strain, O(br)-O(br) interactions are attractive and favor filling of neighbor br sites. These interaction effects are relatively modest in absolute magnitude but are large enough to influence the ability of the RuO2(110) surface to promote oxidation of relatively weak reductants, such as NO and C2H4.