Electronic, structural, and optical properties of crystalline yttria

The electronic structure of crystalline Y2O3 is investigated by first-principles calculations within the local-density approximation (LDA) of the density-functional theory. Results are presented for the band structure, the total density of states (DOS), the atom-and orbital-resolved partial DOS. effective charges, bond order, and charge-density distributions. Partial covalent character in the Y-O bonding is shown, and the nonequivalency of the two Y sites is demonstrated. The calculated electronic structure is compared with a variety of available experimental data. The total energy of the crystal is calculated as a function of crystal volume. A bulk modulus B of 183 Gpa and a pressure coefficient B' of 4.01 are obtained, which are in good agreement with compression data. An LDA band gap of 4.54 eV at Gamma is obtained which increases with pressure at a rate of dE(g)/dP = 0.012 eV/Gpa at the equilibrium volume. Also investigated are the optical properties of Y2O3 up to a photon energy of 20 eV. The calculated complex dielectric function and electron-energy-loss function are in good agreement with experimental data. A static dielectric constant of epsilon(O)= 3.20 is obtained. It is also found that the bottom of the conduction band consists of a single band, and direct optical transition at Gamma between the top of the valence band and the bottom of the conduction band may be symmetry forbidden.