Dielectric Response of Yttria–Zirconia Ordered Solids Within Density-Functional Theory in the Random-Phase Approximation

Despite the fact that yttria-stabilized zirconia has been studied experimentally by optical and electron energy-loss spectroscopies, a first-principles theoretical interpretation of the dielectric response and electronic excitations is still lacking. The present study reports calculations of the complex dielectric function, reflectivity spectrum and electron energy-loss function of two ordered yttria–zirconia compounds: Zr6Y2O15 and Zr3Y4O12. The adopted methodology is based on linear-response theory with a semilocal density functional and the random-phase approximation including local-field effects. Comparisons with existing experimental data show an acceptable agreement showcasing how the different yttria content affects dielectric properties and spectra lineshapes. Strong discrepancies with experimental data are mainly confined to the low-energy part of the optical spectra and concern both the peak positions and the lineshape intensities. The onset of the optical absorption is considerably underestimated from the calculations owing to the well-known deficiency of semilocal density functionals to describe the quasiparticle band gaps. The energy-loss spectra, instead, are reproduced extremely well provided that local-field effects are included in the response functions. These effects are particularly important for the description of the semicore Zr–4p and Y–4p excitations, which dominate for higher energies (>30 eV) in the valence region.