Ab initio hybrid DFT calculations of BaTiO3 bulk and BaO-terminated (001) surface F-centers

Using a supercell model and a hybrid B3PW exchange-correlation functional, we have performed first principles calculations for the F-center in the BaTiO 3 bulk and on the BaO-terminated (001) surface. We find that two Ti atoms nearest to the bulk F-center are repulsed, while nearest eight oxygen and four barium atoms relax toward the oxygen vacancy (by 1.06, 0.71 and 0.08% of the lattice constant [Formula: see text], respectively). The magnitudes of atomic displacements around the F-center located on the BaO-terminated (001) surface in most cases (except for Ti) are larger than those around the bulk F-center (0.1, 1.4 and 1.0% of [Formula: see text], respectively). Our calculated BaTiO 3 bulk [Formula: see text]–[Formula: see text] bandgap of 3.55 eV is in an acceptable agreement with the respective experimental bandgap value of 3.2 eV. The pristine BaO-terminated (001) surface [Formula: see text]–[Formula: see text] bandgap (3.49 eV) is reduced with respect to the bulk bandgap value. The bulk and BaO-terminated (001) surface F-center bands in BaTiO 3 matrix are located only at 0.23 eV and 0.07 eV under the conduction band (CB) bottom, indicating that the F-center is a shallow donor. The F-center in the BaTiO 3 bulk contains charge of 1.103[Formula: see text], whereas slightly less charge, only 1.052[Formula: see text], are localized inside the F-center on the BaO-terminated (001) surface. Our calculations demonstrate considerable increase of the chemical bond covalency between the BaTiO 3 bulk F-center and its two nearest Ti atoms equal to 0.320[Formula: see text], and even larger increase for BaO-terminated (001) surface F-center and its nearest Ti atom 0.480[Formula: see text], in comparison to the relevant Ti–O chemical bond covalency in the perfect BaTiO 3 bulk 0.100[Formula: see text]. The difference between F-center formation energy in BaTiO 3 bulk (10.3 eV) and on the BaO-terminated (001) surface (10.2 eV) trigger the segregation of the F-center from the bulk toward the BaO-terminated (001) surface.