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Extensive density-functional theory calculations, and taking into accounttemperature and pressure, affords a comprehensive picture of the behavior andinteraction of oxygen and Ag(111), and provides valuable insight into thefunction of silver as an oxidation catalyst. The obtained phase-diagram revealsthe most stable species present in a given environment and thus identifies (andexcludes) possibly active oxygen species. In particular, for the conditions ofethylene epoxidation, a thin oxide-like structure is most stable, suggestingthat such atomic O species are actuating the catalysis, in contrast to hithertoproposed molecular-like species.

Why is a Noble Metal Catalytically Active? The Role of the O-Ag Interaction in the Function of Silver as an Oxidation Catalyst