Composition, structure, and stability of (formula presented) as a function of oxygen pressure

Abstract

Using density-functional theory we calculate the Gibbs free energy to determine the lowest-energy structure of a (formula presented) 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 a 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 (formula presented) Together with analogous results obtained previously at the (0001) surface of corundum-structured oxides, these findings on (110) rutile indicate that the stability of nonstoichiometric terminations is a more general phenomenon of transition metal oxide surfaces. © 2001 The American Physical Society.