First-principles calculations of BaZrO3 (001) and (011) surfaces

In an extension of our previous studies of BaTiO3, SrTiO3, and PbTiO3(001), as well as BaTiO3 and SrTiO3(011) surfaces [1-6], I present and discuss the results of calculations of BaZrO3(001) surface relaxation and rumpling with two different terminations (BaO and ZrO2), and BaZrO3(011) polar surface relaxation with three terminations (Ba-, ZrO- and O-terminated, A-type). These are based on hybrid Hartree-Fock and density-functional theory exchange functionals, using Becke's three-parameter method, combined with the nonlocal correlation functionals by Perdew and Wang [7]. According to the results of my calculations, all upper layer atoms for ZrO2- and BaO-terminated BaZrO3(001) surfaces relax inwards. The surface rumpling for the BaO-terminated BaZrO3(001) surface is much larger than for the ZrO2-terminated BaZrO3(001) surface. Both BaO-terminated (1.30 eV) and ZrO2-terminated (1.31 eV) surfaces are stable and energetically equally favourable. Unlike the BaZrO3(001) surface, different terminations of the (011) surface lead to great differences in the surface energies. The A-type O-terminated surface has the lowest energy (2.32 eV). The Ba-terminated BaZrO3(011) surface has a much higher surface energy of 2.90 eV, while the BaZrO3 ZrO-terminated (011) surface has the highest energy (3.09 eV). I predict a considerable increase of the Zr-O chemical bond covalency near the (011) surface, as compared to both the bulk and the (001) surface.