Composition, structure and stability of RuO_2(110) as a function of oxygen pressure

Physics – Condensed Matter – Materials Science

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12 pages including 5 figures. Submitted to Phys. Rev. B. Related publications can be found at http://www.fhi-berlin.mpg.de/th/

Scientific paper

10.1103/PhysRevB.65.035406

Using density-functional theory (DFT) we calculate the Gibbs free energy to determine the lowest-energy structure of a RuO_2(110) surface in thermodynamic equilibrium with an oxygen-rich environment. The traditionally assumed stoichiometric termination is only found to be favorable at low oxygen chemical potentials, i.e. low pressures and/or high temperatures. At realistic O pressure, the surface is predicted to contain additional terminal O atoms. Although this O excess defines a so-called polar surface, we show that the prevalent ionic model, that dismisses such terminations on electrostatic grounds, is of little validity for RuO_2(110). Together with analogous results obtained previously at the (0001) surface of corundum-structured oxides, these findings on (110) rutile indicate that the stability of non-stoichiometric terminations is a more general phenomenon on transition metal oxide surfaces.

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