Crystal Structure of (H3O)6[(UO2)5(SeO4)8(H2O)5](H2O)5

Crystals of (H₃O)₆[(UO₂)₅(SeO₄)₈(H₂O)₅](H₂O)₅ were prepared from aqueous solutions by evaporation. The crystal structure [monoclinic system, space group P2₁/m, a = 13.835(2), b = 13.4374(16), c = 14.310(3) Å, β = 108.004(14)°, V = 2530.1(7) Å ³] was solved by the direct method and refined to R ₁ = 0.090 for 4409 reflections with |F _hkl ≥ 4σ|F _hkl |. The structure is based on [(UO₂)₅(SeO₄)₈(H₂O)₅]⁶⁻ layers arranged parallel to the (101) plane; these layers have a unique topological structure. The U(1)O₆(H₂O) and U(3)O₆(H₂O) linked through selenate groups form chains running along [ [`1]\bar 1 01] direction. The chains are combined in layers by U(2)O₆(H₂O) bipyramids. The layers are linked with each other by hydrogen bonds through the H₂O and H₃O⁺ groups located between the layers.     

Crystal Structure of (H3O)2[(UO2)2(SeO4)3(H2O)2](H2O)3.5

Crystals of (H₃O)₂[(UO₂)₂(SeO₄)₃(H₂O)₂](H₂O)_3.5 were prepared from aqueous solutions by evaporation. The crystal structure [monoclinic system, space group P2₁/m, a = 11.9402(11), b = 13.6452(14), c = 13.7271(12) Å, β = 109.436(7)°, V = 2109.1(3) ų] was solved by the direct method and refined to R ₁ = 0. 048 (wR ₂ = 0. 082) for 3677 reflections with |F _hkl |F _hkl |. The structure consists of [(UO₂)₂(SeO₄)₃(H₂O)₂]₂₋ layers arranged parallel to the (010) plane. The layers are formed by uranium and selenium coordination polyhedra sharing common vertices and are linked with each other by hydrogen bonds through the H₂O and H₃O⁺ groups arranged between the layers. __________ Translated from Radiokhimiya, Vol. 47, No. 5, 2005, pp. 412–414. Original Russian Text Copyright ? 2005 by Krivovichev, Kahlenberg.     

Synthesis and study of compounds A 2I (UO2)2Si5O13 · 3H2O (AI = Na, K)

Sodium and potassium diuranyl pentasilicates were prepared by precipitation from a solution followed by hydrothermal treatment. The structure, properties, and thermal behavior of these compounds were studied by X-ray diffraction, IR spectroscopy, and thermal analysis. Original Russian Text ? N.G. Chernorukov, A.V. Knyazev, A.A. Sazonov, 2007, published in Radiokhimiya, 2007, Vol. 49, No. 2, pp. 114–115.     

Large-scale fabrication of H2(H2O)Nb2O6 and Nb2O5 hollow microspheres

Hollow micro-sized H₂(H₂O)Nb₂O₆ spheres constructed by nanocrystallites have been successfully synthesized via a bubble-template assisted hydrothermal process. In the reaction process, H₂O₂ acts as a bubble generator and plays a key role in the formation of the hollow structure. An in situ bubble-template mechanism has been proposed for the possible formation of the hollow structure. The spherelike assemblies of these H₂(H₂O)Nb₂O₆ nanoparticles have been transformed into their corresponding pseudohexagonal phase Nb₂O₅ through a moderate annealing dehydration process without destroying the hierarchical structure. Optical properties of the as-prepared hollow spheres were investigated. It is exciting that the absorption edge of the hollow Nb₂O₅ microspheres shifts about 18 nm to the violet compared with bulk powders in the UV/vis spectra, indicating its superior optical properties.     

Alkaline earth titanoniobates with a layer structure : A0.5H(TiNbO5)2.nH2O

The ion exchange properties of the layer oxide HTiNbO₅ in the presence of alkaline earth acetate solution A(CH₃COO)₂ has been investigated. The maximum exchange rate increases with the size of the A ion, leading to the hydrates : Ba(TiNbO₅)₂.4H₂O, Sr_0.75H_0.50(TiNbO₅)₂.4H₂O and Ca_0.50H(TiNbO₅)₂.4H₂O. The minimum exchange rate corresponds to the definite compounds A_0.5H(TiNbO₅)₂.4H₂O, labelled 4W-hydrates. The study of the thermal stability of the 4W-hydrates leads to the hydrates A_0.5H(TiNbO₅)₂.2H₂O and A_0.5H(TiNbO₅)₂.H₂O, and finally to the dehydrated oxides A_0.5H(TiNbO₅)₂. The reversibility of the ion exchange reaction and of the hydration phenomenon has been studied. The X-ray diffraction study of these compounds shows that the structure of the (TiNbO₅) layers is conserved whatever the nature of the A ion and of the hydrate may be. The structural evolution versus water content and size of the A ions is discussed.     

Investigation on growth and characterization of a new inorganic NLO material: Zinc sulphate (ZnSO4:7H2O) doped with Magnesium Sulphate (MgSO4:7H2O)

Single crystal of Zinc sulphate doped with Magnesium sulphate, a nonlinear material, was grown from aqua solution by slow evaporation method at room temperature. Good quality single crystals were grown by slow evaporation technique (four weeks) and the crystals subjected to single crystal X-ray diffraction and FT-IR analyses to confirm the formulation of new crystals. The TGA and DTA reveal that the material has good thermal stability. The UV-Vis spectrum confirms that the material has wide optical transparency and the existence of the second harmonic generation has also been ascertained by Kurtz powder method.     

不确定度和稳定度达10-18量级的钙离子光频标

主要回顾了中国科学院精密测量科学与技术创新研究院在液氮低温钙离子光频标的物理系统设计、不确定度评估与稳定度的优化与测量等方面的工作。液氮低温系统为钙离子创造了液氮的温度环境（~ 80 K）,极大降低了钙离子光频标的黑体辐射频移,使钙离子光频标的系统不确定度降至3.0 × 10^-18,成为第五种不确定度进入10^-18的原子/离子光频标体系。为了优化钙离子光频标的稳定度,将钟激光频率参考在Ramsey条纹上,并引入了参考条纹判定算法及自动寻峰算法,使钙离子光频标可长期稳定运行,长期稳定度达到6.3 × 10^-18@524 000 s。     

Computational study of interaction of bromine ions with clusters (O2)6(H2O)50 and (O3)6(H2O)50

Interaction of bromine ions with water clusters that have absorbed the molecules of oxygen and ozone is studied using a molecular-dynamics simulation of flexible molecules. The cases of location of Br⁻ ions on the surface and in the bulk of the cluster are described. Water clusters with ozone molecules remain stable during their interaction with the Br⁻ ions, while oxygen molecules are found to evaporate from the cluster when Br⁻ ions appear in its bulk. In the presence of Br⁻ ions, the infrared spectra of systems with O₃ molecules are observed to be intensified. The intensities of the IR spectra with O₂ molecules may both increase and decrease depending on the arrangement of the Br⁻ ions. The Raman spectra are sensitive to the appearance of Br⁻ ions only for systems that contain oxygen molecules. As a result of interaction with the Br⁻ ions, the power of IR radiation emitted by the clusters can not only increase, but also decrease.     

Reaction of π-Ti2O(PO4)2·2H2O with molten alkali nitrates: Synthesis of the fibrous materials π-M0.5H0.5TiOPO4 (M = Na, K)

Powder X-ray diffraction data for π-Ti₂O(PO₄)₂·2H₂O (π-TiP) is indexed in a monoclinic cell [a=5.067(4), b=10.898(3), c=14.533(8) Å, β=96.0(1)°]. Structural correlations with other titanium phosphates are discussed. The reaction of π-TiP with molten MNO₃ (M=Na, K) originates new metal phases with a KTP-type formula, π-M_0.5H_0.5TiOPO₄. These compounds maintain the fibrous morphology of their precursor. The reactions are monitored by thermogravimetric analysis. Thermal decomposition of the novel compounds is described.     

Evidence for the non-existence of a bragg reflection superlattice in K2Pt(CN)4Br0.3·3H2O and K2Pt(CN)4Cl0.3·3H2O

An extensive and careful search for superlattice reflections in K₂Pt(CN)₄Br_0.3·3H₂O and K₂Pt(CN)₄Cl_0.3·3H₂O has yielded no evidence for an enlarged cell. Six individual crystals obtained via different preparative methods, from solutions at several pH values from 2 to 10, and subjected to a variety of conditions of temperature and humidity have been examined. All samples gave identical cells and nearly identical diffraction patterns. Two samples gave a single weak non-integral 00l neutron reflection which is not explainable by order contamination or double diffraction.     

Synthesis and conductivity of solid high-proton conductor H5GeW10MoVO40·21H2O

A new solid high-proton conductor decatungstomolybdovanadogermanic heteropoly acid (HPA) H₅GeW₁₀MoVO₄₀·21H₂O has been synthesized for the first time by stepwise acidification and stepwise addition of solutions of the component elements. The product was characterized by chemical analysis, potentiometric titration, IR, UV, XRD and TG-DTA. The IR, UV and XRD indicate that H₅GeW₁₀MoVO₄₀·21H₂O possesses the Keggin structure. The TG-DTA curve shows the sequence of water loss in the acid, the amount of the loss, as well as the thermostability. The results of AC impedance measurement show that its proton conductivity is 3.58 × 10⁻⁴ S cm⁻¹ at 18 °C and the activation energy for proton conduction is 31.82 kJ/mol.     

Synthesis of (Na2O,PbO)-Nb2O5, (Na2O,BaO)-Nb2O5, and (K2O,SrO)-Nb2O5 thin films using sol-gel method

Homogeneous pore-free Ba₂NaNb₅O₁₅, KSr₂Nb₅O₁₅, and 2·Na₂O-PbO-6·Nb₂O₅ thin films were fabricated on sapphire substrates using the sol-gel technique. By controlling the gelation and coating process, thickness of thin films fabricated was controllable from ~ 40 nm to ~ 10 μm. Synthesized thin films possessed highly preferred orientated microstructure. Another advantage of this method is the subsequent heat treatment temperature dramatically decreased compared with other methods. This increases stoichiometry control and makes the large scale fabrication more feasible and efficient.     

Synthesis and structural studies of a new potassium uranyl selenate K(H5O2)[(UO2)2(SeO4)3(H2O)] with strongly deformed layers

Single crystals of a new uranyl selenate, K(H₅O₂)[(UO₂)₂(SeO₄)₃(H₂O)] (I), were prepared by isothermal evaporation at room temperature. The crystal structure of I was solved by the direct method (space group P2₁/c; a = 11.456(2), b = 10.231(1), c = 14.809(2) ?; β = 101.901(4)°, V = 1698.4(4) ?³; Z = 4) and refined to R ₁ = 0.0547 (wR ₂ = 0.0825) for 3375 reflections with |F _o| ≥ 4σ _F . The structure of I is based on layers of the composition [(UO₂)₂(SeO₄)₃(H₂O)]²⁻. The charge of the inorganic layer is compensated by potassium and oxonium ions located in the interlayer space. Each potassium ion is coordinated by seven oxygen atoms belonging to uranyl selenate layers, including uranyl oxygen atoms, which leads to bending of uranyl selenate structural elements.     

The preparation and growth of pure single crystals of K2Pt(CN)4Br0.3·3H2O and K2Pt(CN)4Cl0.3·3H2O

The preparation of pure single crystals of K₂Pt(CN)₄Br_0.3·3H₂O and K₂Pt(CN)₄Cl_0.3·3H₂O has been investigated. Crystals with reproducible d.c. conductivity and dielectric constants were obtained only when the mixed valence platinum salt contained one halide. The bromide complex was particularly susceptible to contamination by chloride, and a preparation scheme is presented which excludes the unwanted halide. The best quality crystals were grown by slow evaporation of solutions which were 1 molar in urea and 0.1 molar in the appropriate potassium halide.     

Flower-like microparticles and novel superparamagnetic properties of new binary Co1/2Fe1/2(H2PO4)2·2H2O obtained by a rapid solid state route at ambient temperature

A new binary Co_1/2Fe_1/2(H₂PO₄)₂·2H₂O was synthesized by a simple, rapid and cost-effective method using CoCO₃-Fe(c)-H₃PO₄ system at ambient temperature. Thermal treatment of the obtained Co_1/2Fe_1/2(H₂PO₄)₂·2H₂O at 600 °C yielded as a binary cobalt iron cyclotetraphosphate CoFeP₄O₁₂. The FTIR and XRD results of the synthesized Co_1/2Fe_1/2(H₂PO₄)₂·2H₂O and its final decomposed product CoFeP₄O₁₂ indicate the monoclinic phases with space group P2₁/n and C2/c, respectively. The particle morphologies of both binary metal compounds appear the flower-like microparticle shapes. Room temperature magnetization results show novel superparamagnetic behaviors of the Co_1/2Fe_1/2(H₂PO₄)₂·2H₂O and its final decomposed product CoFeP₄O₁₂, having no hysteresis loops in the range of ±10,000 Oe with the specific magnetization values of 0.045 and 12.502 emu/g at 10 kOe, respectively. The dominant physical properties of the obtained binary metal compounds (Co_1/2Fe_1/2(H₂PO₄)₂·2H₂O and CoFeP₄O₁₂) are compared with the single compounds (M(H₂PO₄)₂·2H₂O and M₂P₄O₁₂; where M = Co, Fe), indicating the presence of Co ions in substitution position of Fe ions.     

Study on structural phase transitions and relaxation processes of Cs2Co(SO4)2·6H2O and Cs2Zn(SO4)2·6H2O crystals

The structural phase transitions and relaxation processes of Cs₂Co(SO₄)₂·6H₂O and Cs₂Zn(SO₄)₂·6H₂O single crystals were investigated, with the phase transitions of both crystals being determined from NMR data. The spin–lattice relaxation time, T₁, of the ¹³³Cs nucleus in two crystals undergoes a significant change near the phase transition temperature, T_C, and these changes coincide with the changes in the splitting of the ¹³³Cs resonance lines. The variations in the temperature dependence for the splitting of the ¹³³Cs resonance lines and T₁ near T_C are related to changes in the symmetry of surrounding Cs⁺. In addition, the ¹³³Cs T₁ of Cs₂Co(SO₄)₂·6H₂O, which contains paramagnetic ions, was found to be shorter than that of Cs₂Zn(SO₄)₂·6H₂O. This relaxation time is inversely proportional to the square of the magnetic moment of the paramagnetic ions. The differences between the ¹³³Cs T₁ of these compounds are probably due to the differences between the electronic structures of their metal ions.     

Crystal structures, thermal analysis and IR investigations of (C4H14N2O)SO4 and (C4H14N2O)SO4·H2O

Crystals of 2(2-ammonium ethyl ammonium)ethanol sulfate monohydrate: (C₄H₁₄N₂O)SO₄·H₂O abbreviated as AEESM, and 2(2-ammonium ethyl ammonium)ethanol sulfate: (C₄H₁₄N₂O)SO₄ abbreviated as AEES, have been prepared and grown at room temperature. These materials have the following unit cell dimensions (C₄H₁₄N₂O)SO₄·H₂O: a = 16.116(6), b = 7.411(3), and c = 15.750(6) Å; (C₄H₁₄N₂O)SO₄: a = 8.1142(2), b = 10.6632(4), c = 9.9951(4) Å, and β = 99.433(3)°. Their space groups are Pbca and P2₁/c, respectively. The structures of these compounds have been determined by single-crystal X-ray data analysis. The AEESM structure is built up from infinite inorganic chains parallel to the b axis linked via Ow-H?O hydrogen bonds. These chains are interconnected by organic groups so as to build layers perpendicular to the c direction. The structure of AEES consists of a three-dimensional network of H-bonds connecting all its components. In the present work the crystal structures, thermal behavior and IR analysis of these two new compounds are described.     

Progress in the realization of a frequency standard at 192.1 THz(1560.5 nm) using 87Rb D2-line and second harmonicgeneration

Second harmonic generation of a 192.1 THz semiconductor distributed feedback (DFB) laser is achieved using a KNbO₃ crystal in a resonant ring cavity. Optical feedback from this cavity is used to stabilize the laser frequency and reduce its linewidth. A second harmonic power of 5.5 μW is generated with 38 mW incident on the cavity. We use the second harmonic signal to observe saturated absorption lines and orientation signals in rubidium vapor. Injection-locking of a 780 nm Fabry-Perot laser using the second harmonic signal is also demonstrated. With this scheme, we observe saturated absorption lines in rubidium     

On the proton conductor (H3O)Zr2(PO4)3

The compound HZr₂(PO₄)₃ was converted to (H₃O)Zr₂(PO₄)₃ by refluxing in water for 12 or more hours. The water is lost above 150°C to regenerate the original triphosphate. The hydronium ion phase is rhombohedral with hexagonal axes of a = 8.760(1) and $\text{c}\text{= 23.774(4)}\text{A}\text{?}$. Proton conduction in these compounds was investigated by an ac impedance method over the frequency range 5Hz – 10MHz. The activation energy for (H₃O)Zr₂(PO₄)₃ in the temperature range of 25 to 150°C was 0.56eV while the corresponding value for HZr₂(PO₄)₃ (125 – 300°C) was 0.44eV.     

Synthesis and characterization of a new 2,4,6-triaminopyridinium dihydrogendiphosphate dihydrate (C4H8N5)2H2P2O7·2H2O

Structural properties of the 2,4,6-triaminopyridinium dihydrogendiphosphate dihydrate are discussed on the basis of an X-ray structure investigation. (C₄H₈N₅)₂H₂P₂O₇·2H₂O is monoclinic, C2/c, with a = 10.414(1) Å, b = 13.365(1) Å, c = 13.736(2) Å, β = 98.39(4)°, and Z = 4. The structure has been solved by a direct method and refined to a reliability R factor of 0.0375 (R_w = 0.0961) using 2751 independent reflections. The structural arrangement can be described as inorganic infinite ribbons, , spreading along the c direction; the organic groups, [C₄H₈N₅]⁺, link the precedent ribbons, via their hydrogen bonds, to form a three-dimensional network. The present work, deals with crystal structure, thermal behavior and IR analysis of this new compound.