Density fluctuations as door-opener for diffusion on crowded surfaces.

How particles can move on a catalyst surface that, under the conditions of an industrial process, is highly covered by adsorbates and where most adsorption sites are occupied has remained an open question. We have studied the diffusion of O atoms on a fully CO-covered Ru(0001) surface by means of high-speed/variable-temperature scanning tunneling microscopy combined with density functional theory calculations. Atomically resolved trajectories show a surprisingly fast diffusion of the O atoms, almost as fast as on the clean surface. This finding can be explained by a "door-opening" mechanism in which local density fluctuations in the CO layer intermittently create diffusion pathways on which the O atoms can move with low activation energy.