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First principles calculations of the atomic and electronic structure of F centers in bulk and on the (001) surface of SrTiO3

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The atomic and electronic structure, formation energy, and the energy barriers for migration have been calculated for the neutral O vacancy point defect F center in cubic SrTiO3 employing various implementations of density functional theory DFT. Both bulk and TiO2-terminated 001 surface F centers have been considered. Supercells of different shapes containing up to 320 atoms have been employed. The limit of an isolated single oxygen vacancy in the bulk corresponds to a 270-atom supercell, in contrast to commonly used supercells containing 40–80 atoms. Calculations carried out with the hybrid B3PW functional show that the F center level approaches the conduction band bottom to within 0.5 eV, as the supercell size increases up to 320 atoms. The analysis of the electronic density maps indicates, however, that this remains a small-radius center with the two electrons left by the missing O ion being redistributed mainly between the vacancy and the 3d z2 atomic orbitals of the two nearest Ti ions. As for the dynamical properties, the calculated migration energy barrier in the low oxygen depletion regime is predicted to be 0.4 eV. In contrast, the surface F center exhibits a more delocalized character, which leads to significantly reduced ionization and migration energies. Results obtained are compared with available experimental data.

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CARRASCO RODRÍGUEZ, Javier, ILLAS I RIERA, Francesc, LÓPEZ, Núria (lópez alonso), KOTOMIN, E. a., ZHUKOVSKII, Yu. f., EVARESTOV, R. a. (robert aleksandrovich), MASTRIKOV, Yu. a., PISKUNOV, S., MAIER, J.. First principles calculations of the atomic and electronic structure of F centers in bulk and on the (001) surface of SrTiO3. _Physical Review B_. 2006. Vol. 73, núm. 6, pàgs. 064106-1-064106-11. [consulta: 31 de gener de 2026]. ISSN: 0163-1829. [Disponible a: https://hdl.handle.net/2445/10830]

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