Thermochemistry of Solid-state Formation, Structure, Optical, and Luminescent Properties of Complex Oxides Eu2MeO6 (Me - Mo, W), Eu2W2O9: A Combined Experimental and DFT Study.

Complex oxides Eu2MeO6 (Me - Mo, W), Eu2W2O9 were obtained by a solid-phase reaction between binary oxides. The thermodynamic and kinetic mechanisms of the reaction processes were established using a variety of physical-chemical methods. All compounds obtained in this work crystallize in the low-symmetry monoclinic system, forming complex framework structures, which determine a set of very valuable physical-chemical properties. Comparison of experimental Kubelka-Munk functions and DFT- calculated absorption spectra shows adequate agreement and reveals the origin of the fundamental absorption. In addition, the deficiency in DFT calculations in the part of mutual contribution of CTBs of Mo-O and W-O, from one side, and Eu-O contributions, from the other side, is reported. Calculations of absorption spectra are shown to be superior to band structure analysis in the determination of optical band gaps. Additionally, luminescent properties of Eu2MeO6 and Eu2W2O9 compounds were investigated. These studies provide a better understanding of the electronic and optical properties of the compounds Eu2MeO6 and Eu2W2O9, along with their potential applications in various areas.

Negative Thermal Expansion in the Polymorphic Modification of Double Sulfate ß-AEu(SO4)2 (A-Rb+, Cs+).

New polymorphic modifications of double sulfates ß-AEu(SO4)2 (A-Rb+, Cs+) were obtained by the hydrothermal method, the structure of which differs significantly from the monoclinic modifications obtained earlier by solid-state methods. According to single-crystal diffraction data, it was found that the compounds crystallize in the orthorhombic system, space group Pnna, with parameters ß-RbEu(SO4)2: a = 9.4667(4) Å, b = 13.0786(5) Å, c = 5.3760(2) Å, V = 665.61(5) Å3; ß-CsEu(SO4)2: a = 9.5278(5) Å, b = 13.8385(7) Å, c = 5.3783(3) Å, V = 709.13(7) Å3. The asymmetric part of the unit cell contains one-half Rb+/Cs+ ion, one-half Eu3+ ion, both in special sites, and one SO42- ion. Both compounds exhibit nonlinear negative thermal expansion. According to the X-ray structural analysis and theoretical calculations, the polarizing effect of the alkali metal ion has a decisive influence on the demonstration of this phenomenon. Experimental indirect band gaps of ß-Rb and ß-Cs are 4.05 and 4.11 eV, respectively, while the direct band gaps are 4.48 and 4.54 eV, respectively. The best agreement with theoretical calculations is obtained using the ABINIT package employing PAW pseudopotentials with hybrid PBE0 functional, while norm-conserving pseudopotentials used in the frame of CASTEP code and LCAO approach in the Crystal package gave worse agreement. The properties of alkali ions also significantly affect the luminescent properties of the compounds, which leads to a strong temperature dependence of the intensity of the 5D0 → 7F4 transition in ß-CsEu(SO4)2 in contrast to much weaker dependence of this kind in ß-RbEu(SO4)2.