Comparative ab initio study of electronic, optical and chemical bonding properties of pyrochlores, Y2B2O7 (B=Ti4+, Sn4+)

Abstract

The nature of chemical bonding that is responsible for the disparity between the optical properties of the impurity ions in the pyrochlores, Y2Sn2O7 and Y2Ti2O7 has been quantified by computing in the density functional theory framework the structural, physical electronic and optical properties of the host lattices. The partial density of states calculations and the estimation of the Mulliken charges indicate the significant different behavior of the oxygen ions in the two different crystallographic positions (48f and 8b) of the pyrochlore lattice. The hybridization between the filled 2p orbital of oxygen ion on the 48f site (O48f2−) and the empty 3d0 orbital of Ti4+ results in an anomalously lower charge on O48f2− in Y2Ti2O7 when compared with that in Y2Sn2O7 with filled Sn4+ 4d10 orbital. This covalent mixing is chiefly responsible for the disparity between the optical properties of the impurity ions in Y2Sn2O7 and Y2Ti2O7. Additional information on the nature of chemical bonding is provided by calculating the influence of external hydrostatic pressure on the interatomic distances and the elastic properties of the pyrochlores.