Influence of Pb adatom on adsorption of oxygen molecules on Pb(111) surface: a first-principles study

Using first-principles calculations, we systematically study the influence of Pb adatom on the adsorption and the dissociation of oxygen molecules on Pb(111) surface, to explore the effect of a point defect on the oxidation of the Pb(111) surface. We find that when an oxygen molecule is adsorbed near an adatom on the Pb surface, the molecule will be dissociated without any obvious barriers, and the dissociated O atoms bond with both the adatom and the surface Pb atoms. The adsorption energy in this situation is much larger than that on a clean Pb surface. Besides, for an adsorbed oxygen molecule on a clean Pb surface, a diffusing Pb adatom can also change its adsorption state and enlarge the adsorption energy for O, but it does not make the oxygen molecule dissociated. And in this situation, there is a molecule-like PbO2 cluster formed on the Pb surface.