RESUMEN

We report optical absorption and luminescence measurements in pure and trivalent neodymium (Nd3+) doped LaVO4 crystals up to 25 GPa. Nd3+ luminescence has been employed as a tool to follow the structural changes in the crystal. We also present band-structure and crystal-field calculations that provide the theoretical framework to accurately explain the observed experimental results. In particular, both optical absorption and luminescence measurements evidence that a phase transition takes place close to 12 GPa. They also provide information on the pressure dependence of the band-gap as well as the emission lines under compression. We found drastic changes in the optical properties of LaVO4 when the phase transition to a BaWO4-II structure occurs, which can be related to changes in the coordination number of vanadium ions and in the local sites of Nd3+. Reported results are analyzed in comparison with those of previous X-ray diffraction and Raman experiments, as well as with the features of related compounds. For the first time, a consistent picture is reported explaining the behavior of the optical and electronic properties of LaVO4 at high-pressures.

RESUMEN

We investigate the lattice dynamical and dielectric properties of MgO single crystals and powders by measurements in the mid- and far-infrared frequency region under high pressures, ranging up to 21.7 GPa. The shift of the restrahlen region is used to determine the pressure dependence of the transverse and longitudinal optical modes. The analysis of the refractive index in the mid- and far-infrared region allowed us to obtain the pressure behavior of the static and electronic dielectric constants. The transverse effective charge slowly decreases under high pressure, reflecting the stability of MgO. As a consequence, the pressure dependence of the static and electronic dielectric constants is mainly determined by the pressure dependence of the polar phonon frequency and Penn gap, resulting in a pronounced decrease of the former and a moderate decrease of the latter.

Asunto(s)

RESUMEN

We present the results of x-ray diffraction and x-ray absorption spectroscopy experiments in CuAlO(2) under high pressure. We discuss the polarization dependence of the x-ray absorption near-edge structure at the Cu K-edge. XRD under high pressure evidences anisotropic compression, the a-axis being more compressible than the c-axis. EXAFS yields the copper-oxygen bond length, from which the only internal parameter of the delafossite structure is deduced. The combination of anisotropic compression and the internal parameter decrease results in a regularization of the AlO(6) octahedra. The anisotropic compression is related to the chemical trends observed in the lattice parameters when Al is substituted by other trivalent cations. Both experiments evidence the existence of an irreversible phase transition that clearly manifests at 35 ± 2 GPa. The structure of the high-pressure polymorph could not be determined, but it implies a change of the Cu environment, which remains anisotropic. Precursor effects are observed from the lowest pressures, which are possibly related to crystal breaking at a submicroscopic scale with partial reorientation of the crystallites.