We present a first principles thermodynamic study of O ad-atom and vacancy formation on the AO- and BO2-terminated (001) surfaces of the PbTiO3 (PTO) and LaMnO3 (LMO) cubic perovskites Our results show that, owing to the highly energetically unfavorable nature of O vacancy formation on these surfaces, O vacancies appear only at high temperatures and practically irrelevant low pressures on the (T, p) surface phase diagram. In contrast, effortless formation of O ad-atoms on the surfaces is encountered at practically achievable pressures and temperatures. Above room temperature and close to atmospheric pressures, we predict clean PbO and TiO2-terminated (001) PTO surfaces as the stable surface phases while partially or fully O ad-atom covered surfaces are found to be more stable for LMO. These results are consistent with the observation that LMO is far more active towards oxidation catalysis than PTO.
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Pilania, G., Ramprasad, R. Thermodynamics of Oxygen Chemistry on PbTiO3 and LaMnO3 (001) Surfaces. MRS Online Proceedings Library 1309, 1013090323 (2011). https://doi.org/10.1557/opl.2011.731