ABSTRACT
The compression process in the α-phase of europium trimolybdate was revised employing several experimental techniques. X-ray diffraction (using synchrotron and laboratory radiation sources), Raman scattering and photoluminescence experiments were performed up to a maximum pressure of 21 GPa. In addition, the crystal structure and Raman mode frequencies have been studied by means of first-principles density functional based methods. Results suggest that the compression process of α-Eu2(MoO4)3 can be described by three stages. Below 8 GPa, the α-phase suffers an isotropic contraction of the crystal structure. Between 8 and 12 GPa, the compound undergoes an anisotropic compression due to distortion and rotation of the MoO4 tetrahedra. At pressures above 12 GPa, the amorphization process starts without any previous occurrence of a crystalline-crystalline phase transition in the whole range of pressure. This behavior clearly differs from the process of compression and amorphization in trimolybdates with [Formula: see text]-phase and tritungstates with α-phase.
ABSTRACT
Polycrystalline samples of α-phase samarium molybdate were prepared by solid-state synthesis and used for x-ray diffraction (from 300 to 1000 K) and dielectric spectroscopy (from 500 to 900 K and from 10(2) to 10(6) Hz). The electrical conductivity follows the universal dielectric response, and three different regimes of conduction (with semiconductor, polaronic, and ionic characteristics) were ascribed. The polaronic mechanism in the range from 600 to 810 K was probed using the overlapping large polaron model. Above 810 K, the application of scaling laws suggests an ionic conductivity. The thermal dependence of the lattice parameter a shows three different trends in correspondence with the three conduction regimes observed. An analysis using adapted symmetry modes facilitated the Rietveld refinement and the study of the thermal dependence of the distortion arising from the oxygen displacements. We suggest that the transversal displacements of oxygen atoms in Sm-O-Mo bridges joined to the elongation of tetrahedra can help to explain this anomalous behavior. From the calculated bond-valence contour maps, new sites for the oxygen atoms, at higher temperatures, were detected which favor oxygen motion and would then be related to the ionic conduction. This correlation has been compared and extended to α-Eu(2)(MoO(4))(3).
