Restructuring of the Pt3Sn(111) surfaces induced by atomic and molecular oxygen from first principles.

The surface restructuring of Pt3Sn(111) induced by oxygen chemisorption is examined by means of density-functional theory calculations. Molecular and atomic oxygen chemisorption is investigated on the two available terminations of the bulk alloy—(2×2) and (3×3)R30°—these two surfaces differing by the tin content and the nature of chemical sites. An extensive geometric, energetic, and vibrational analysis is performed including the influence of oxygen coverage in the case of atomic adsorption. For molecular adsorption, regular structures have been obtained for both surfaces with a clear effect of tin on the stability of the adsorption forms. In contrast, for atomic adsorption, two oxygen chemical states are found. In particular, a peculiar surface restructuring, involving the formation of a network of SnO2 species, appears for large oxygen coverage. However the two terminations present discrepancies for the restructuring mechanism all along the oxygen coverage increase. All these results are supported by a...