The crystal structure of tetrammine copper sulphate Cu(NH3)4SO4·H2O

The crystal structure of tetrammine copper sulphate was determined. The orthorhombic unit cell with dimensions a=12.12, b=10.66, c==7.07 Åcontains four molecules of Cu(NH ₃)₄ SO ₄.H ₂ O, the space group is Pbnm (D _2h ¹⁶ ).The atomic coordinates were determined from the projections of the Patterson function and the electron density onto the (001) and (010) planes. The complex cation Cu(NH ₃)₄ ⁺⁺ is approximately planar, the groups of NH ₃ are linked by co-valent bonds to the central Cu atom. The average distance of the groups of NH ₃,which are approximately at the corners of a square surrounding the central Cu atom, is 2.90 Å, the distance Cu-NH ₃,corresponding to the co-valent bond, is 2.05 Å.     

茂金属配合物[(eat5-C5H4R)Mo(CO)3 ]2(R: SiMe3 ,Si2Me5)的电子结构研究

运用G98W ,采用Lanl2dz基组 ,对茂金属配合物 [(eat5 C5H4R)Mo(CO) 3 ]2 (R :SiMe3 ,Si2 Me5)进行从头算研究 ,探讨配合物结构单元的稳定性、分子轨道能量、原子净电荷布居规律 ,以及一些前沿分子轨道的组成特征等 ,结果表明 ,标题配合物结构在能量上是稳定的 ,作为结构单元而存在 .     

[Cu(en)2][KFe(CN)6]·H2O的磁性分析

合成了氰根桥联配合物[[Cu(en)2][KFe(CN)6].H2O,使用元素分析、红外光谱等对配合物进行了表征。首次通过对该配合物的磁化率测定表明金属离子通过氰根传递弱反铁磁作用,计算求得分子磁体χmT的实验值与理论值。并根据Curie-Weiss定律拟合获得居里常数C=0.42cm3.K.mol-1和顺磁居里温度=-0.54K。     

The crystal structure of meta-zeunerite Cu(UO2)2(AsO4)2⋅8 H2O

The structure of the mineral zeunerite (deposits at Rotava near Kraslice, Ore Mountains) was determined. The tetragonal unit cell, having the dimensionsa=7.10₅Å andc=17.70₄Å, contains two structure units of Cu(UO₂)₂(AsO₄)₂8H₂O. The space group isP4₂/nmc. The distribution of the atoms in the unit cell was determined from the Patterson projectionP(vw) and by means of (F ₀-F _c) synthesis. Meta-Zeunerite has a layer type structure. The sheets [(UO₂)(AsO₄)] are separated by layers containing the cations (Cu(H₂O)₄)²⁺ and molecules of water. The uranium is coordinated octahedrally with six oxygen atoms at distances: U-O₁ 1.94 Å, U-O₂ 1.78 Å, U-O₃₍₄₎ 2.18 Å (4×). The uranyl radical O₁-U-O₂ is linear. In the tetrahedron AsO₄ the interatomic distances are As-O 1.77 Å and the bond angles 102°, 102°, 113° and 113°. Each oxygen atom of the tetrahedron AsO₄ is simultaneously bonded to the uranium atom. The bond angle As-O-U is 137°. The layers [(UO₂)₂(AsO₄)] are bonded together by the cations (Cu(H₂O)₄)²⁺. The distances Cu-O₁ and Cu-O₂ are 2.55 and 2.58Å respectively. The structural changes during hydration and dehydration are explaned.

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- Cu(UO₂)₂(AsO₄)₂8 H₂O

( , ). =7,10₅ Å,=17,70₄ Å Cu(UO₂)₂(AsO₄)₂8 ₂O. P4₂/nmc. P(v w) (F ₀-F _c) . . , [(UO₂)(AsO₄)], , [u(₂)₄]²⁺ . : U-O₁ 1,94 Å, U-O₂ 1,78 Å, U-O₃₍₄₎ 2,18 Å ( ). ₁-U-₂. AsO₄ As- 1,77 Å -102°, 102°, 113° 113°. AsO₄ . As--U 137°. [(UO₂)₂(AsO₄)] [u(₂O)₄]²⁺. u-O₁ 2,55 Å, u-O₂ 2,58 Å. .

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In conclusion the author thanks T. Veselská for assistance in the calculations and workers of the National Museum in Prague, and primarily Dr. ípek, for supplying the sample. The experimental work was carried out at the Department of Physics of the Natural Science Faculty of Komenský University.     

Isotopic effect in Brillouin light-scattering spectra of a Cs5H3(SO4)4 · xH2O crystal

A Brillouin scattering study of the behavior of hypersonic longitudinal acoustic phonons in crystalline pentacesium trihydrogen tetrasulfate Cs₅H₃(SO₄)₄ · xH₂O (PCHS) and its deuterated analog Cs₅D₃(SO₄)₄ · xD₂O (DPCHS) at temperatures ranging from 420 to 120 K is reported. The effect of deuteration on the crystal lattice dynamics is investigated. The differences in the behavior of hypersonic acoustic phonons in the PCHS and DPCHS crystals suggest the existence of a hydrogen isotope effect in both the high-and low-temperature phases. A possible model of the isotopic effect in the high-temperature phase is discussed. An analysis is made of the acoustic response of the PCHS and DPCHS crystals in the region of the transition to the glasslike phase.     

Low-temperature phase transitions and dynamics of ammonium in (NH4)3H(SO4)2 and [(NH4)1−x Rbx]3H(SO4)2 crystals

The (NH₄)₃H(SO₄)₂ and [(NH₄)_0.82Rb_0.18]₃H(SO₄)₂ crystals are investigated by dielectric spectroscopy, inelastic incoherent neutron scattering (IINS), and neutron powder diffraction. A comparative analysis of the data obtained is given. It is shown that the phase transitions II ? III, III ? IV, IV ? V, and V ? VII in the (NH₄)₃H(SO₄)₂ crystal are accompanied by changes in the orientation ordering of the NH ₄ ⁺ ions. In the [(NH₄)_0.82Rb_0.18]₃H(SO₄)₂ crystal, these phase transitions are completely suppressed and the long-range order inherent in the II phase is retained over the entire temperature range covered (6–300 K). It is revealed that this crystal at the temperature T _g≈70 K undergoes a transition to the dipole glass phase, which is attended by “freezing” the orientation disordering of the ammonium ions.     

适用于全光开关的[(C3H7)4N][Au(C3S5)2]三阶非线性光学性质研究

合成了一种金属有机配合物[(C3H7)4N][Au(C3S5)2].配制了浓度为1×10-3 mol/L的[(C3H7)4N][Au(C3S5)2]/乙腈溶液,并用旋涂法制备了掺杂浓度质量比为1%的[(C3H7)4N][Au(C3S5)2]/PMMA复合薄膜.运用Z扫描方法,分别研究了样品溶液和薄膜在波长为1064nm...     

适用于全光开关的[(C3H7)4N][Au(C3S5)2]三阶非线性光学性质研究

合成了一种金属有机配合物[(C3H7)4N][Au(C3S5)2].配制了浓度为1×10－3 mol/L的[(C3H7)4N][Au(C3S5)2]/乙腈溶液,并用旋涂法制备了掺杂浓度质量比为1%的[(C3H7)4N][Au(C3S5)2]/PMMA复合薄膜.运用Z扫描方法,分别研究了样品溶液和薄膜在波长为1 064 nm,脉宽为20 ps条件下的三阶非线性光学性质.研究发现薄膜的三阶非线性极化率χ(3)比溶液高出三个数量级.其中,薄膜的非线性折射率n2为－1.76×10－15 m2/W、三阶非线性极化率χ(3)为9.37×10－10 esu.结果表明,该材料在全光开关方面具有潜在的应用价值.     

Investigation of the EPR parameters of the rhombic Cu2+ center in (NH4)2Mg(SO4)2·6H2O single crystal

The electron paramagnetic resonance (EPR) parameters (g factors g_x, g_y, g_z and hyperfine structure constants A_x, A_y, A_z) for Cu²⁺ in (NH₄)₂Mg(SO₄)₂·6H₂O (DHMS) crystal are theoretically investigated using the high-order perturbation formulas of these parameters. In the calculations, the ligand orbital and spin–orbit coupling for the impurity Cu²⁺ are taken into account; the required crystal-field parameters are estimated from the superposition model which enables correlation of the crystal-field parameters and hence the EPR parameters with the local structure of the impurity center. The ligand orbital and the spin–orbit coupling contributions are included on the basis of the cluster approach. Based on the calculation, the theoretical EPR parameters show good agreement with the observed values. The results are discussed.     

混配配合物[Co(cpida)(C7H5N2)2]·C7H5N2·5H2O

在溶液中用N-(邻苯甲酸基)-亚氨基二乙酸、苯并咪唑和Co(Ac)2·4H2O进行自组装合成了标题三元金属混配配合物.用元素分析、红外光谱、单晶衍射对配合物的组成和结构进行了表征,确定配体N-(邻苯甲酸基)-亚氨基二乙酸中的3个羧基为单齿形式与中心金属钴离子配位.     

The phase diagram of single crystal [(CH3)4N]2CuBrxCl4−x solid solutions

Differential scanning calorimetry (DSC) and X-ray measurements give evidence on a complete miscibility within the solid solution system [(CH₃)₄N]₂CuBr_xCl_4−x. In addition to the known phase sequences of pure components, some new phases appear for intermidiate concentrations. Out of five triple points observed in the phase diagram, one seems to be a Lifshitz point between a paraelectric, an incommensurate and a ferroelectric phase.     

配位超分子[Cu(phen)(H2O)2·SO4]的合成、结构及表面光电压光谱

采用水热合成法得到了新颖结构的配位超分子[Cu(phen)(H2O)2.SO4]。通过X射线单晶衍射、红外光谱(IR)、紫外光谱(UV-VIS-NIR)及荧光光谱进行了测定和分析指认结构分析表明:标题化合物中Cu离子的配位模式分为两种,与phen分子中的2个N原子和水分子中2个O原子是通过配位键直接配位的;与硫酸根离子中的2个O原子的配位是采取Cu离子与O原子之间形成氢键,该氢键使Cu离子和硫酸根离子中的2个O原子处于亚配位状态,因此使Cu离子处于扭曲的八面体几何构型中。晶体中存在着大量的氢键将化合物连成了1D双链结构。利用表面光电压光谱(SPS)和场诱导表面光电压光谱(FISPS)研究了化合物的表面光电行为。化合物的SPS在300～800nm范围内呈现出明显的2个正的光伏响应带。FISPS的结果显示化合物呈现出一定的p-型半导体的特征。     

EPR studies of Cu2+ ion in CdK2 (SO4)2·6H2O single crystals

The EPR spectra of Cu²⁺ in CdK₂(SO₄)₂·6H₂O crystals have been studied at 77 K and 300 K in three (bc, a¹c and a¹b) planes. The angular variation spectra showed that the Cu²⁺ ion enters the Cd²⁺ site in the lattice. The principal g and A values, covalency parameter (α'²), mixing coefficients (α and β) and Fermi-contact term (K) have been evaluated from the EPR analysis. The ground-state wave function of the Cu²⁺ ion has been constructed using the α'², α and β values, and the signs for the hyperfine coupling constants are also determined. The covalency value indicates the percentage of unpaired spin density present at the metal (Cu²⁺) d orbital. The nature of the distortion present in the lattice is obtained from the values of the mixing coefficients.     

Electron paramagnetic resonance of Gd3+ in Nd2(SO4)3 · 8H2O single crystal

Electron paramagnetic resonance study has been carried out in Gd3+ doped single crystals of Nd₂(SO₄)₃·8H₂0 at three different temperatures. Two magnetic complexes exhibiting orthorhombic or lower symmetry are found and the results have been fitted to a suitable spin-Hamiltonian. The ten “best fit” parameters are obtained from two computer programs. Zero-field splittings of Gd3+ have been deduced from spin-Hamiltonian parameters and are compared with those observed directly by Bogle and Symmons. Fine forbidden transitions ∥ΔM_s∥ I > 1 are analyzed using numerical solution of the Hamiltonian matrix.     

[MnHg(SCN)4(H2O)2]·2C4H9NO(MMTWD)晶体的光谱分析

根据商群对称性分析法对MMTWD晶体的振动模作了理论计算.计算结果显示,通过实验可观察到的拉曼散射峰和红外反射带应分别不超过297和148个.运用实验的手段,分别测定晶体的拉曼光谱和红外光谱,给出了MMTWD晶体在50～3 000 cm-1范围内的拉曼光谱图和400～4 000 cm-1范围里的红外光谱图,并对光谱中的谱线作了指认.给出了MMTWD晶体的分子结构示意图,最终确定MMTWD晶体结构为三维网状结构,说明在众多新型光功能材料当中MMTWD晶体是一种更适合生长成较大尺寸且稳定性较好的非线性光学晶体,在光电子领域中具有良好的应用前景.     

Second-order electroelastic tensor of cubic KAl(SO4)2·12H2O

The second-order electroelastic tensor {Z_ijklmn}, which describes the variation of the elasticity tensor under the influence of an electric field in centrosymmetric crystals, has been completely determined on cubic KAl(SO₄)₂·12H₂O by measuring the electric-field-induced shift of ultrasonic resonance frequencies. The state of resonance was detected by diffraction of light through the standing ultrasonic grating formed in the state of resonance. The necessary resolution of 10^-9 for the relative frequency change was achieved employing a phase-sensitive amplification of the modulated part of the diffracted light.All main components of the second-order electroelastic tensor possess values of about -15·10^-10 NV^-2. The negative sign indicates a general weakening of the elastic bonds by an electric field. A distinct anisotropy is observed in accordance with point symmetry m3.     

Spin-glass behavior and magnetic splitting in molecular magnetic materials {[N(n-C4H9)4][MIIFeIII(C2O4)3]}n (M = Co, Mn)

The mixed valence character and the antiferromagnetic coupling in the molecular magnetic materials {[N(n-C₄H₉)₄][M^IIFe^III(C₂O₄)₃]}_n (M = Co, Mn) were investigated by Mössbauer spectroscopy and magnetic measurements. In the material {[N(n-C₄H₉)₄][CoFe(C₂O₄)₃]}_n, the appearence of the spin-glass phase transition temperature and the magnetic phase transition under zero-field-cooled AC magnetic measurements were studied in the temperature range 5–100 K. In the Mössbauer spectra of {[N(n-C₄H₉)₄][MnFe(C₂O₄)₃]} a magnetic splitting was observed below 30 K. The appearance of the magnetic splitting indicates the occurrence of magnetic ordering in this complex. The hyperfine parameters show that the electronic state of iron is high-spin Fe³⁺.     

光谱法研究Ni[(C4H9O)2PS2]2与氮碱的加合反应(Ⅱ)

用光谱法研究了NiL2 在 30℃时与乙胺、正丙胺、正丁胺和正戊胺在乙醇溶液中的加合反应。伯胺类氮碱 (B)与NiL2 生成 1∶1的五配位NiL2 ·B和 1∶2的六配位NiL2 ·B2 两种加合物。所有五配位NiL2 ·B和六配位NiL2 ·B2 加合物的吸收光谱分别由NiNS4和NiN2 S4发色基团所产生。实验测定了反应的平衡常数lgβn 及加合分子数n。lgβn 随胺类碱度 pKa值增加而增大 ,且可以经验公式来描述lgβ1 =- 9 6 9+1 15pKa ;lgβ2 =- 18 73+2 2 8pKa     

糖精钴水合物[Co(C7H4NO3S)2(H2O)4]·2H2O的合成及晶体结构

以糖精钠(sac-Na)、丙氨酸和硝酸钴为原料合成得到糖精钴琥珀色块状晶体,采用红外、X射线单晶衍射对配合物进行了表征,该晶体属单斜晶系,空间群为P21/c,晶胞参数为:a=0.79269(5)nm,b=1.61407(10)nm,c=0.77026 (5) nm,α=90°,β=99.695(7)°,Ⅴ=0.97145 (11) nm3,Z=2,Dc=1.817g/cm3,F(000)=546,R=0.0278.结构分析表明,中心Co离子与4个O原子和两个N原子配位,处于四角双锥八面体配位环境中,4个水分子在赤道平面上与Co离子配位,晶胞中还包含有2个游离的结晶水,形成了含6个水分子的结晶物.