Phase equilibria in the ErPO4–K3PO4 system

The phase equilibria occurring in the ErPO₄–K₃PO₄ system were investigated by the thermal analysis, FTIR, and X-ray powder diffraction methods. On the basis of obtained results, the related phase diagram is proposed. This system includes one intermediate compound, K₃Er(PO₄)₂; the double phosphate melts incongruently at 1355 °C and occurs in two polymorphic forms; transformation β/α-K₃Er(PO₄)₂ proceeds at 420 °C. The eutectic occurs at the composition of 58.5 wt% K₃PO₄, 41.5 wt% ErPO₄ at 1317 °C.     

Phase equilibria in the YPO4–Rb3PO4 system

The phase equilibria occurring in the YPO₄–Rb₃PO₄ system were investigated by thermoanalytical methods, X-ray powder diffraction, and ICP-OES. On the basis of the obtained results, its phase diagram is proposed. It was found that the system includes two intermediate compounds Rb₃Y(PO₄)₂ and Rb₃Y₂(PO₄)₃. The Rb₃Y(PO₄)₂ compound melts congruently at 1300 °C. The Rb₃Y₂(PO₄)₃ orthophosphate was previously unknown. This intermediate compound is high-temperature unstable and decomposes within the temperature range 1300–1330 °C to YPO₄ and Rb₃Y(PO₄)₂. The decomposition process is irreversible. It was found that the Rb₃Y₂(PO₄)₃ orthophosphate is isostructural with Rb₃Yb₂(PO₄)₃ and crystallizes in the cubic system (a = 1.70226 nm).     

Phase Equilibria in the System YPO4–K3PO4–KMgPO4

The phase equilibria in the part of the ternary system YPO₄–K₃PO₄–Mg₃(PO₄)₂ over the composition range YPO₄–K₃PO₄–KMgPO₄ were examined and determined by differential thermal analysis, X-ray powder diffraction and microscopic analysis in reflected light. This revised version was published online in August 2006 with corrections to the Cover Date.     

Phase equilibria in the system Rb3PO4–Ba3(PO4)2

The system Rb₃PO₄–Ba₃(PO₄)₂ was investigated by thermoanalytical methods, X-ray powder diffraction, ICP, and FT-IR. On the basis of the obtained results its phase diagram was proposed. For this system with one intermediate compound, BaRbPO₄, we found that this compound melts congruently at 1700 °C, exhibits a polymorphic transition at 1195 °C and is high-temperature unstable. Also, the intermediate compound was subject to gradual decomposes to Ba₃(PO₄)₂ (the solid phase) and vaporization (with conversion of phosphorus and rubidium oxides into vapor phase). We also found that Rb₃PO₄ melts congruently at 1450 °C and shows a polymorphic transition at 1040 °C. Regarding Ba₃(PO₄)₂, we have confirmed that it melts congruently at 1605 °C and exhibits a polymorphic transition at 1360 °C.     

Defects in Tm^3＋／Yb3＋—doped YVO4 Crystals

<正>The microscopic defects have been investigated for crystal Tm3+/Yb3+:YVO4. These defects mainly include the inclusions (solid inclusions, bubbles and inclusions of the liquid phase), dendrites and growth stripes. They are caused by in-pure raw materials, unstable growth conditions, super-cooling component and so on. Tm3+/Yb3+:YVO4 crystals of large size and excellent optical quality are grown by improving the growth conditions to eliminate these defects.     

Hyperfine interactions in the A3Φ4 and X3Φ4 states of iridium monofluoride, IrF

Laser induced-fluorescence spectra of the 1-0 band of the A(3)Φ(4)-X(3)Φ(4) transition of iridium monofluoride, IrF, have been obtained at near natural linewidth resolution using supersonic molecular beam techniques. The spectra show a complex, clearly resolved hyperfine structure which has significant contributions from the magnetic and quadrupole hyperfine terms in (193)Ir and (191)Ir, both with I = 3/2, and the fluorine magnetic hyperfine term (I = 1∕2). The spectra of both (193)IrF and (191)IrF isotopologues have been assigned and analyzed. The hyperfine structure was interpreted with the aid of atomic hyperfine parameters, which were used to determine the configurational composition of the ground state and to estimate the individual molecular hyperfine parameters.     

5D3-5D4 cross-relaxation of Tb3+ in α-GdOF

The ⁵D₃-⁵D₄ cross-relaxation of Tb³⁺ in α-GdOF has been investigated by analysis of the ⁵D₃ decay curve. It is shown that the relaxation is electric dipole-dipole in character. The relaxation rate has been evaluated in the temperature region between 4.2 K and room temperature. The temperature dependence of the relaxation rate points to the thermal population of a higher-lying ⁷F₆ or ⁵D₃ level.     

Sodium ion-conducting solid electrolytes in the system Na3PO4Na2SO4

In the system Na₃PO₄Na₂SO₄, the high-temperature, cubic γ form of Na₃PO₄ forms an extensive range of solid solutions: Na_3−x(P_1−xS_x)O₄, 0 < x < (0.57 to 0.70, depending on temperature). For compositions in the range x = ca. 0.33 to 0.57, these γ solid solutions are thermodynamically stable at all temperatures. The conductivity of the γ solid solutions increases with increasing x and reaches a maximum at x = 0.5 to 0.6, with values of 2 × 10⁻⁵ ohm⁻¹ cm⁻¹ at 100°C, rising to 1.3 × 10⁻² ohm⁻¹ cm⁻¹ by 300°C; this conductivity increase with x is attributed to an increase in the sodium ion vacancy concentration, associated with the solid solution mechanism Na + PS. The phase diagram for the system Na₃PO₄Na₂SO₄ is given together with lattice parameters of the γ solid solutions.     

Formation of 3-acyloxy-γ-butyrolactones from 4-pentenols in vanadium-catalyzed oxidations

O-Acyl derivatives of 3-hydroxy-γ-butyrolactone are formed in up to 20% yield as by-products from 1-alkyl- and 1-phenyl-substituted 4-pentenols and tert-butyl hydroperoxide (TBHP) in vanadium-catalyzed synthesis of (tetrahydrofuran-2-yl)-methanols. The lactones are secondary products formed from (tetrahydrofuran-2-yl)-methanols via hydrogen atom abstraction in positions 4 and 5, as derived from experiments starting from deuterium-labeled alkenols. Stereocenters at tetrahydrofuran carbon 2 and the proximate hydroxyl carbon of the alkanol side chain retain configuration in the course of oxidative tetrahydrofuran conversion. In an atmosphere of nitrogen or argon, no γ-butyrolactone formation occurs, pointing to dioxygen as terminal oxidant for the secondary oxidation. Adding cyclohexa-1,4-diene or γ-terpinene to a solution of a 4-pentenol, TBHP, and a vanadium catalyst exposed to air inhibits formation of γ-butyrolactones. A third approach to prevent γ-butyrolactones from being formed in oxidative 4-pentenol cyclization uses cis-2,6-bis-(methanol)-piperidine instead of N-salicylidene-ortho-aminophenol as tridentate auxiliary for the vanadium catalyst.     

Surface chemistry of nanoscale Fe_3O_4 dispersed in magnetic fluids

The interaction between stabilizers and nanoparticles is one of the important factors to prepare stable magnetic fluids. The magnetic nano-size Fe3O4 core with single domain and the average grain size around 8-12 nm were prepared by chemical precipitation method. The O/Fe molar ratio of the particle surface was measured by X-ray photoelectron spectroscopy (XPS). The heat effects of stabilizers ad- sorption on nanoparticles were measured by solution calorimetry. The excess amount of oxygen was possibly the result of the hydroxygen formed on the surface of the nanoparticles. The heat effects showed that compounds containing carboxyl groups can be adsorbed chemically on magnetite by forming chemical bonds. The other stabilizers involving NH-groups, such as polyethylene-imine, can be adsorbed physically. The exothermic value is about half of the former case.     

Analysis of the ν2 :ν3 + ν4 Fermi resonance in CH3CN isotopic species in solution

Infrared bands due to ν₃ + ν₄, ν₂, ν₃ and ν₄ were recorded for the species CH₃CN, ¹³CH₃CN, CH₃¹³CN and CH₃C¹⁵N in the solvents carbon tetrachloride, chloroform, benzene, pyridine and dimethyl sulphoxide. Values of W₂₃₄ were extracted by the modified Winther method, which are slightly less, 11.2–11.9 cm⁻¹, than the value in the gas, 12.15 cm⁻¹. Relative intensity measurements of ν₃ + ν₄ and ν₂ in CCl₄ are compatible with an unperturbed intensity ratio, I_{ν3 + ν4}/ I_ν2 of ∼ 0.03. The fallibility of the infrared intensity method for determining W, and the need for precise frequency data in the Winther method, are stressed.     

Optical-transition Probability of Tm^3＋ Ions in Tm^3＋／Er^3＋：YVO4 Crystal

1INTRODUCTIONThelasersoperatedataround2mmwavelengthhavegainedmuchinterestbecauseofvariousappli-cations,e.g.(1)groundorspaceremotesensingforLIDARandmetrology,(2)medicalapplicationssinceliquidwaterhasastrongabsorptionbandnear2mm,and(3)eyesafelaser[1,2].The2…     

Spin-orbit Coupling and Intersystem Crossing in 4H-Pyran-4-thione： CASSCF//TD-B3LYP Study

The intersystem crossing channels of gaseous 4H-pyran-4-thione were investigated using the CASSCF//TD-B3LYP methods and group theory. Using the effective one-electron spin-orbit Harniltonian, the strengths of spin-orbit coupling were estimated, which plays an essential role in the spin transitions between different spin states. Calculated results show that phosphorescence and non-radiative decay via intersystem crossing to the So state are concurrent processes occurring at the T1 state. A rapid depletion of the S1 state via intersystem crossing to the T1 state can be mediated by the T2 state, if spin relaxation is fast within the triplet levels. Our calculated results are in close agreement with experimental observations.     

Cation distribution in (M′,M)3Se4: I. (Cr,Ti)3Se4

The cation distribution to the two crystallographic cation sites of the Cr₃S₄ structure was determined in CrTi₂Se₄ and TiCr₂Se₄ by the high-resolution neutron diffraction, using Rietveld analysis. The result showed that the Cr ions preferentially occupy the 2(a) sites. The magnetic properties of the (Cr_xTi_1−x)₃Se₄ system were also measured and discussed in relation to the selective substitution of metal ions resulting from the site preference of each ion.     

Cation distribution in (M′, M)3Se4: II. (V,Ti)3Se4 and (Cr,V)3Se4

The cation distribution among the two crystallographic cation sites of the Cr₃S₄ structure was determined in VTi₂Se₄ and VCr₂Se₄ by high-resolution neutron diffraction, using Rietveld analysis. The results showed a considerable disorder but they nevertheless revealed the site preference of V atoms for the 2(a) site in both compounds. The compositional changes of the lattice parameters and the transition temperatures to the CdI₂-type structure in (V_xTi_1−x)₃Se₄ and (Cr_xV_1−x)₃Se₄ were compared with those in (Cr_xTi_1−x)₃Se₄ and (Fe_xCr_1−x)₃Se₄, and discussed from the viewpoint of the site preference of the cation.     

Solid Solutions in The Cr2O3–α-Sb2O4–MoO3 System

DTA and XRD methods used to examine the Cr₂O₃–α-Sb₂O₄–MoO₃ system have shown that a substitution solid solution of MoO₃ in CrSbO₄ is formed. A study of all the theoretically possible solid solution models has pointed to the fact that Mo⁶⁺ ions are incorporated into the CrSbO₄ crystal lattice, in the place of Sb⁵⁺ ions and the compensation of redundant charges takes place through cation vacancies arising in an Sb⁵⁺ sub-lattice. The solubility limit for MoO₃ in CrSbO₄ does not exceed 25.00 mol%. CrSbO_4(s.s.) is stable to ~1320°C. This revised version was published online in July 2006 with corrections to the Cover Date.     

Theoretical Analyses of 4f11 →4f105d Excitation Spectra of Er3+ Doped in LiYF4

Spectral terms and J-spectral multiplet of low-spin 4f^105d configuration of Er^3 were obtained with the method of ligand field theory. According to the selection rules for dipole transitions, the excitation spectra of Er^3 doped in LiYF4 in vacuum ultraviolet region (120～160nm) of the spectrum were theoretically interpreted by applying the crystal field model, and the six bands were assigned to the spin-allowed transitions from the ground state (^4I15/2) to J-spectral multiplet of low-spin 4f^105d configuration of Er^3 ion.