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Abstract

The photoemission electron microscope (PEEM) makes it possible to image a surface via its work function. On a CO-covered Pt(100) surface, we prepared oxygen islands which appear dark in the PEEM image due to their higher work function. As the surface is heated to temperatures above 650 K we observe the conversion of these dark islands into very bright ones with work functions much lower than even that of the clean surface arising from an inverted dipole moment of oxygen atoms beneath the surface. We found an activation energy for this conversion of about 15 kcal/mol. Partially transformed oxygen islands were used to study the reactivity and the formation of this species further. CO and H₂ both react with subsurface oxygen rather slowly, while at the interface between the subsurface and the chemisorbed phase, both adsorbents accelerate the conversion of parts of the remaining oxygen atoms towards the subsurface state. In contrast, additional oxygen adsorption does not contribute to a further transformation. We propose a qualitative microscopic model for the formation of subsurface oxygen based on experimental evidence.