Identification of a laterally mobile state during CO adsorption

We have investigated CO adsorption at 300 K on ∼ 1.5 atomic layer thick Pd films on a Mo(110) surface by high-resolution core level photoemission. We describe how high-resolution core level spectroscopy may be utilized to study the influence of laterally mobile states on the sticking probability of molecules on such a laterally heterogeneous surface. The present Pd films are laterally heterogeneous in the sense that the additional ∼ 0.5 atomic Pd layer forms mesoscopic one-layer thick islands on top of the first Pd layer. At 300 K, CO chemisorbs on these two-layer thick islands but not on the one-layer parts of the film. The rate at which these two-layer islands are filled by CO molecules as the surface is exposed to CO is found to be consistent with a picture where CO molecules that initially impinge on the one-layer parts of the surface enter a laterally mobile state and diffuse to the two-layer islands and adsorb there. This mobile state is in many respects similar to a classical precursor state.