The adsorption of atomic oxygen on unreconstructed Pt{100}-(1 x 1) and reconstructed Pt{100}-(5 x 1) was modelled using density-functional theory in an attempt to understand the relative stability of the unreconstructed phase as a function of oxygen coverage. The calculations showed that, at zero temperature, the (5 x 1) was more stable than the unreconstructed (1 x 1) phase at zero oxygen coverage. However, oxygen absorption on the Pt{100}-(5 x 1) phase removed the reconstruction, reversing the phase stability. Using thermochemical analysis, desorption of oxygen corresponding to a temperature near 730K was shown; consistent with experimentally observed desorption peaks for oxygen covered (1 x 1) surfaces. These results had ramifications for the understanding of the full Pt{100}(1 x 1) → Pt{100}-hex-R0.7° surface phase transition.

Lifting the Pt{100} Surface Reconstruction through Oxygen Adsorption - a Density Functional Theory Analysis. N.A.Deskins, J.Lauterbach, K.T.Thomson: Journal of Chemical Physics, 2005, 122[18], 184709