Modeling the noble metal/TiO2 (110) interface with hybrid DFT functionals: A periodic electrostatic embedded cluster model study
The interaction of Aun and Ptn (n=2,3) clusters with the stoichiometric and partially reduced rutile TiO2 (110) surfaces has been investigated using periodic slab and periodic electrostatic embedded cluster models. Compared to Au clusters, Pt clusters interact strongly with both stoichiometric and reduced TiO2 (110) surfaces and are able to enhance the reducibility of the TiO2 (110) surface, i.e., reduce the oxygen vacancy formation energy. The focus of this study is the effect of Hartree–Fock exchange on the description of the strength of chemical bonds at the interface of Au/Pt clusters and the TiO2 (110) surface. Hartree–Fock exchange helps describing the changes in the electronic structures due to metal cluster adsorption as well as their effect on the reducibility of the TiO2surface. Finally, the performance of periodic embedded cluster models has been assessed by calculating the Pt adsorption and oxygen vacancy formation energies. Cluster models, together with hybrid PBE0 functional, are able to efficiently compute reasonable electronic structures of the reduced TiO2surface and predict charge localization at surface oxygen vacancies, in agreement with the experimental data, that significantly affect computed adsorption and reaction energies.
Published in Journal of Chemical Physics, Volume 133, Issue 164703, 2010.
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The following article appeared in
Ammal, S. C. & Heyden, A. (2010). Modeling the noble metal/TiO2 (110) interface with hybrid DFT functionals: A periodic electrostatic embedded cluster model study. The Journal of Chemical Physics, 133, 164703. http://dx.doi.org/10.1063/1.3497037
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