First-principles calculations of the atomic and electronic structure of SrZr03 and PbZr03 (001) and (011) surfaces

We present the results of calculations of surface relaxations, rumplings, energetics, optical band gaps, and charge distribution for the SrZrO 3 and PbZrO 3 (001) and (011) surfaces using the ab initio code CRYSTAL and a hybrid description of exchange and correlation. We consider both SrO(PbO) and ZrO 2 terminations of the (001) surface and Sr(Pb), ZrO, and O terminations of the polar SrZr0 3 and PbZrO 3 (011) surfaces. On the (001) surfaces, we find that all upper and third layer atoms relax inward, while outward relaxations of all atoms in the second layer are found with the sole exception of the SrO-terminated SrZr0 3 (001) surface second layer O atom. Between all (001) and (011) surfaces the largest relaxations, more than 15% of the bulk lattice constant, are for the Sr- and Pb-terminated SrZr0 3 and PbZrO 3 (011) surface upper layer Sr and Pb atoms. Our calculated surface rumpling for the SrO- and PbO-terminated SrZrO 3 and PbZrO 3 (001) surfaces (6.77 and 3.32% of a 0 ) are by a factor of ten larger than the surface rumpling for the ZrO 2 -terminated (001) surfaces (—0.72 and 0.38% of a 0 , respectively). In contrast to the surface rumpling, the (001) surface energies are comparable and in the energy range from 0.93 eV/cell for the ZrO 2 -terminated PbZrO 3 surface to 1.24 eV/cell for the ZrO 2 -terminated SrZr0 3 surface. In contrast to the (001) surface, different terminations of the SrZr0 3 and PbZr0 3 (011) surfaces lead to very different surface energies ranging from 1.74 eV/cell for the Pb-terminated PbZrO 3 (011) surface to 3.61 eV/cell for the ZrO-terminated SrZr0 3 (011) surface. All our calculated (011) surface energies are considerably larger than the (001) surface energies. Our calculated optical band gap for the SrZrO 3 bulk, 5.31 eV, is in fair agreement with the experimental value of 5.6 eV. All our calculated optical band gaps for the SrZr0 3 and PbZr0 3 (001) and (011) surfaces are reduced with respect to the bulk. We predict a considerable increase in the Zr-O chemical bond covalency near the SrZrO 3 and PbZrO 3 (011) surfaces as compared both to the bulk and to the (00 1) surface.