Thermodynamics of Oxygen Chemistry on PbTiO3 and LaMnO3 (001) Surfaces


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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  1. 1.

    Properties and Applications of Perovskite Type Oxides, ed. L. J. Tejuca and J. L. G. Fierro (Marcel Dekker: New York, 1993).

    Google Scholar 

  2. 2.

    M. A. Pena and J. L. G. Fierro, Chem. Rev. 101, 1981 (2001).

    CAS  Article  Google Scholar 

  3. 3.

    G. Kresse and J. Furthmuller, Phys. Rev. B 54, 11169 (1996).

    CAS  Article  Google Scholar 

  4. 4.

    P. E. Blochl, Phys. Rev. B 50, 17953 (1994).

    CAS  Article  Google Scholar 

  5. 5.

    R. Martin, Electronic Structure: Basic Theory and Practical Methods (Cambridge University Press, New York, 2004).

    Google Scholar 

  6. 6.

    G. Pilania and R. Ramprasad, Surf. Sci. 604, 1889 (2010).

    CAS  Article  Google Scholar 

  7. 7.

    B.G. Shirane and R. Repinsky, Acta Cryst. 9, 131 (1956).

    CAS  Article  Google Scholar 

  8. 8.

    J. Rodryguez-Carvajal, M. Hennion, F. Moussa and A. H. Moudden, Phys. Rev. B 57, R3190 (1998).

    Google Scholar 

  9. 9.

    K. Reuter and M. Scheffler, Phys. Rev. B 65, 035406 (2002).

    Article  Google Scholar 

  10. 10.

    K. Reuter and M. Scheffler, Phys. Rev. B 68, 045407 (2003).

    Article  Google Scholar 

  11. 11.

    J. Rogal, K. Reuter, and M. Scheffler, Phys. Rev. B 75, 205433 (2007).

    Article  Google Scholar 

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Correspondence to Ghanshyam Pilania.

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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).

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