Vibrational spectroscopy at very high pressures. Part 35.1 A Raman study of K2M(CN)4, (M = Zn,Cd, Hg)

Each of the complex cyanides K₂M(CN)₄, (M = Zn, Cd, Hg), shows two high pressure first-order phase transitions which have been characterized using Raman spectroscopy. The phase changes are at 1.5 and 8.5 kbar for M = Hg, 3 and 8 kbar for M = Cd, and 4 and 14 kbar for M = Zn. It is concluded that, for each material, phase II has the trigonally-distorted spinel structure of room temperature Rb₂Hg(CN)₄, whilst phase III is probably of the hausmanite type (a tetragonally-distorted spinel).     

A resistance minimum and the electronic structures of some one-dimensional Pt-complexes at high pressures

The effect of pressure has been measured up to 650 kbar on the electrical resistance in six one-dimensional Pt-complexes, including two mixed valence ones. SrPt(CN)₄·2H₂O, MgPt(CN)₄·7H₂O and BaPt(CN)₄·4H₂O do not show a resistance minimum, contrary to other d⁸-metal complexes, suggesting a considerable contribution of π¹ orbitals of CN^- ligands to the conduction.     

2-D magnetism

Influence of the spatial dimensionality on magnetic ordering phenomena has been discussed. Recent work on ideal 2 dimensional magnets like Rb₂FeF₄, Rb₂MnF₄, K₂NiF₄, Rb₂Mn_xMg_1-x and K₂CuF₄, K₂Cu_xZn_{1 -x}F₄, MnSt₂ possessing planar antiferro- and ferromagnetism, respectively, has been reviewed with a view to doing planar anisotropy calculations based on the reportedly common orthorhombic structures. Existence of easy axes, easy cones in the plane and first order magnetisation processes (FOMP) in the plane and out of plane in the presence of applied magnetic field can be predicted. The results have been presented in the graphical forms as well.     

Pressure-induced ferroelectricity in {N(CH3)4}2FeCl4

The hydrostatic pressure effect on the stability of phases I, II, III and IV in {N(CH₃)₄}₂FeCl₄ was studied by dielectric and DTA measurements in the temperature and pressure region of -40-30°C and 0–2 kbar. The pressure-induced new phase V found at applied pressures between 0.3 and 1.0 kbar was confirmed to be ferroelectric by the observation of D-E hysteresis loop. These results are compared with those of {N(CH₃)₄}₂XCl₄ (X: Co, Zn and Mn) in this paper.     

The effect of zinc concentration on vacancies jump rate, diffusion coefficient and jump length in Cu-Zn ferrite

Samples with the chemical formula Cu_1−xZn_xFe₂O₄ (x=0.2, 0.4, 0.6, 0.8 and 1) were prepared by the standard ceramic method. The dielectric constant and dielectric loss tangent were studied as a function of vacancy jump rate. The results show that the dielectric constant and dielectric loss tangent decrease with increasing vacancy jump rate. In addition, the electron jump length in the octahedral sites was studied as a function of zinc concentration. The increase in jump length with Zn concentration has been attributed to the substitution of Fe⁺³ for Zn²⁺ at the A-sites, which increases the B-B interaction. The increase of diffusion coefficient with increasing Zn concentration was reinforced by the increase of jump rate.     

用高压显微光谱系统研究(Zn0.85Cd0.15)S:Cu,Al磷光体在流体静压力下施主-受主对的发光

用金刚石对顶砧高压显微光谱系统在室温和1bar—66kbar的流体静压力范围内研究了(Zn_0.85Cd_0.15)S:Cu,Al磷光体的发光峰位置和相对发光强度随压力而变化的规律。随着压力的增加,发射峰值波长迅速移向短波方向,而发射峰值对应的光子能量随压力增加的速率为4.7meV/kbar(38cm^-1/kbar)。这个值比该材料的吸收边随压力增加的速率要小。随着压力的增加,该磷光体的发光峰值相对强度急骤下降,当压力从常压升到66kbar时,发光峰值相对强度下降到原值的6％。这些结果可以用Al³⁺-Cu⁺的施主-受主对模型来解释。本文还估计施主(Al³⁺)和受主(Cu⁺)的激活能之和随压力增加的速率为3.7meV/kbar(30cm^-1/kbar)。 关键词：     

On the structural,optical and electrical properties of Cu2+ doped Zn0.94Cd0.06O nanomaterials

Nanoparticles of Cu²⁺ doped Zn_0.94Cd_0.06O oxide with formula Zn_0.94Cd_0.06-xCu_xO [x = 0.0, 0.03, 0.05] were prepared via sol-gel auto combustion (SGAC) method at pH value of 10. Room temperature X-ray powder diffraction (XRD) patterns confirms that all the synthesized samples were single-phased polycrystalline with wurtzite hexagonal structure (P6₃mc). Crystallite size is estimated from XRD which was found to be 29–40 nm. Using Rietveld refinement of XRD data, the structure, space group and other structure related parameters were confirmed. The nanoparticle formation was confirmed via field emission scanning electron microscopy (FE-SEM) and elemental composition was verified through energy dispersive analysis of X-rays (EDAX). Raman spectroscopy reveals seven active phonon modes for both pristine Zn_0.94Cd_0.06O and Zn_0.94Cd_0.06-xCu_xO [x = 0.03, 0.05]. The oxide formation is also conveyed through Fourier transformation of Infra-red (FTIR) spectroscopy. The bandgap using UV–Vis spectroscopy was found to be about 3.02 eV and 3.09 eV for Zn_0.94Cd_0.06-xCu_xO (x = 0.03, 0.05), 3.14 eV for pristine Zn_0.96Cd_0.06O. The dielectric studies confirmed high dielectric constant for Zn_0.94Cd_0.06O that decreases gradually on increasing Cu²⁺ doping concentration. The impedance analysis of all samples shows non-Debye character with spread of relaxation times.     

Infrared dispersion of potassium zinc chloride

The infrared reflection spectra for the three main polarizations of K₂ZnCl₄ in the orthorhombic commensurate ferroelectric phase are reported at room temperature. Phonon frequencies are assigned to internal and external modes by comparison with K₂SeO₄ and Rb₂ZnCl₄ data. The dielectric constant along the ferroelectric axis is essentially due to the weight of the low-frequency heavily-damped mode.     

Effect of Cd on the structural, magnetic and electrical properties of nanostructured Mn-Zn ferrite

Nanoparticles of Mn_0.5Zn_0.5−xCd_xFe₂O₄ (x=0.0, 0.1, 0.2 and 0.3) have been synthesized by a chemical co-precipitation method. The lattice constant increases with increasing Cd content. X-ray calculations indicate that there is deviation in the cation distribution in the nanostructured spinel ferrite. The dielectric constant and dielectric loss decrease for the samples with Cd content up to x=0.2. However the dielectric constant rises for x=0.3. This is due to an increase in the hopping process at the octahedral (B sites). The dielectric constant increases with increase in temperature, indicating a thermally activated hopping process. The DC resistivity increases with Cd content up to x=0.2 and decreases for Cd content x=0.3. The maximum magnetization of all the samples decreases with increase in Cd content.     

等静压下0.75Pb（Mg1/3Nb2/3）O3-0.25PbTiO3陶瓷的介电性能研究

研究了等静压对0.75Pb（Mg_1/3Nb_2/3）O₃-0.25PbTiO₃（PMN-25PT）陶瓷介电温谱的影响,PMN-25PT剩余极化随等静压变化和等静压压致相变.结果表明,随着压力增加,PMN-25PT的介电峰值温度T_m降低,/+{dT_m}/-{dP}≈-4℃/kbar,极化弛豫增强;剩余极化随压力增加连续减小;介电常数对压力的依赖关系与对温度场的依赖相似,压力诱导PMN-25PT发生弛豫铁电—顺电相变,相变为宽化的渐变过程,频率色散和极化弛豫更加强烈和普遍. 关键词： 铌镁酸铅-钛酸铅 等静压 介电弛豫 压致相变     

Hydrostatic pressure study of the structural phase transitions and superconductivity in single crystals of (Ba1−xKx)Fe2As2 (x=0 and 0.45) and CaFe2As2

We studied the effect of hydrostatic pressure (P) on the structural phase transitions and superconductivity in the ternary and pseudo-ternary iron arsenides CaFe₂As₂, BaFe₂As₂, and (Ba_0.55K_0.45)Fe₂As₂, by means of measurements of electrical resistivity (ρ) in the 1.8-300 K temperature (T) range, pressures up to 20 kbar, and magnetic fields up to 9 T. CaFe₂As₂ and BaFe₂As₂ (lightly doped with Sn) display structural phase transitions near 170 and 85 K, respectively, and do not exhibit superconductivity in ambient pressure, while K-doped (Ba_0.55K_0.45)Fe₂As₂ is superconducting for T<30 K. The effect of pressure on BaFe₂As₂ is to shift the onset of the crystallographic transformation down in temperature at the rate of ~−1.04 K/kbar, while shifting the whole ρ(T) curves downward, whereas its effect on superconducting (Ba_0.55K_0.45)Fe₂As₂ is to shift the onset of superconductivity to lower temperatures at the rate of ~−0.21 K/kbar. The effect of pressure on CaFe₂As₂ is first to suppress the crystallographic transformation and induce superconductivity with onset near 12 K very rapidly, i.e., for P<5 kbar. However, higher pressures bring about another phase transformation characterized by reduced-resistivity, and the suppression of superconductivity, confining superconductivity to a narrow pressure dome centered near 5 kbar. Upper critical field (H_c2) data in (Ba_0.55K_0.45)Fe₂As₂ and CaFe₂As₂ are discussed.     

Special points on the phase diagrams of langbeinites. The case of (x,T)-phase diagram of mixed K2xRb2(1−x)Cd2(SO4)3 crystals

We have studied special points that appear on the (x, T)-phase diagram of mixed K_2xRb_2(1?x)Cd₂(SO₄)₃ crystals. This phase diagram has been constructed issuing from the changes in domain structure occurring in the course of phase transitions. We have found that two triple points on the (x, T)-phase diagram of the above solid solutions are very close to each other in the phase space and can change their places or transform into a quadruple point. These special points are associated with disappearance of ferroelectric phases with the symmetries P1 and P2₁ taking place when Rb₂⁺ are substituted with K₂⁺ ions.     

Adsorption and separation of propane and propylene by porous hexacyanometallates

The separation capability for mixtures of propane and propylene by porous frameworks representatives of transition metal hexacyanometallates was studied from adsorption data under equilibrium conditions at 273.15 K and from inverse gas chromatography profiles at different column temperatures. Samples of two porous solids were considered; Cd₃[Co(CN)₆]₂, which is representative of Prussian blue analogues (cubic structure) with a porous framework related to vacancies for building block, and Zn₃[Co(CN)₆]₂ (rhombohedral phase) where the porous framework results from the tetrahedral coordination for the Zn atoms. The two materials were found to be able for the mixtures separation, with the highest separation ability for the rhombohedral phase under equilibrium conditions but, in dynamic conditions the cubic one shown a better separation, which was ascribed to a kinetic contribution related to a smaller windows size.     

高压下LiKSO4介电和弹性特性的反常及p—T相图

本文通过对不同温度T(150—350K)和压力p(0—10kbar)范围内LiKSO₄晶体介电和弹性性质的研究,发现在室温8.2kbar(对应于升压过程),和4kbar(对应于降压过程)附近介电和弹性系数有突变。我们把它归结为压力诱导的LiKSO₄相转变。这个相变过程伴随着很大的压力滞后现象。本文还给出了LiKSO₄在上述温度和压力范围内的p-T相图。并发现在3.8kbar和281K处存在一个三相点。 关键词：     

Neutron scattering study of the metal-semiconductor phase transition in K2Pt(CN)4Br0.3 ·3D2O under pressure

The elastic scattering associated with the 2k_F instability in the one-dimensional (1-d) conductor K₂Pt(CN)₄Br_0.3 · 3D₂O (KCP) has been studied at the low temperature super lattice point (0.5, 0.5, 3.7) as a function of temperature for different pressures. Within the investigated region between 0 and 11 kbar, we find that the value of 2k_F remains constant at $\text{1.703 c}{}^1$, although the absolute value of 2k_F changes by 1.5%. At the same time the Peierls gap Δ(0) and the interchain correlation length ξ_⊥ (0) decrease. We conclude that the 1-d character of KCP is enhanced under pressure.     

Electrical conduction studies on one-dimensional Cs2[Pt(CN)4](FHF)0.39 and Rb2[Pt(CN)4](FHF)0.40

Variable temperature (300-40 K) 4-probe d.c. conduction studies on Cs₂[Pt(CN)₄](FHF)_0.39 and Rb₂[Pt(CN)₄](FHF)_0.40 are described. In these salts T_3D occurs at a lower temperature than in K₂[Pt(CN)₄]Br_0.3·3H₂O and this is attributed to the absence of an inter-chain network of hydrogen bonded water molecules in the bifluorides.     

Pressure-induced low-temperature transitions in TMMC

Measurements of the pressure dependence of the low-frequency dielectric constant ? and high pressure, low temperature X-ray diffraction photographs on (CH₃)₄ (TMMC) have shown that the low temperature $\text{P2}{}_1\text{aa}$ phase of TMMC transforms to the low temperature $\text{P2}{}_1\text{m}$-like phase of (CH₃)₄ NCdCl₃ (TMCC) at high pressure. The pressure-temperature phase diagram has been deliniated from the triple point at 2.0 kbar and 137° K to lower temperatures, and, from changes in the dielectric constant anomaly, it appears that another triple point may occur at ～ 1.0 kbar and 95° K. The pressure and temperature dependences of ? together with the observed doubling of the unit cell suggest that the $\text{P2}{}_1\text{a}$ low temperature phase of TMMC may be antiferroelectric.     

高x值混晶Hg1-xCdxTe光吸收边的压力效应

采用金刚石对顶砧高压装置,在0—36kbar流体静压力范围和室温条件下测量了高x值的P型碲镉汞混晶Hg_0.3Cd_0.7Te光吸收边及其随压力的变化。300K下Hg_0.3Cd_0.7Te光学能隙的实验值与用经验公式的计算值一致。用最小二乘法拟合不同压力下的实验结果,得到Hg_0.3Cd_0.7Te能隙的一阶压力系数α=8.7×10^-11eV/Pa,与用化学键介电 关键词：     

Structural,electronic and optical properties of CdxZn1 − xS alloys from first-principles calculations

Structural, electronic and optical properties as well as structural phase transitions of ternary alloy Cd_xZn_1 − xS have been investigated using the first-principles calculations based on the density functional theory. We found that the crystal structure of Cd_xZn_1 − xS alloys transforms from wurtzite to zinc blende as Cd content of x=0.83$x=0.83$. Effect of Cd content on electronic structures of Cd_xZn_1 − xS alloys has been studied. The bandgaps of Cd_xZn_1 − xS alloys with wurtzite and zinc blende structures decrease with the increase of Cd content. Furthermore, dielectric constant and absorption coefficient also have been discussed in detail.     

Observation of electromagnetic resonances in crystals of K2Pt (CN)4 Br0.3.3H2O at microwave frequencies

Electromagnetic dielectric resonances in the range 8–11 GHz have been observed in millimeter sized crystals of K₂Pt(CN)₄Br_0.3.3H₂O. This observation results directly from the existence of large dielectric constants; values for the longitudinal and transverse dielectric constants at 4°K are estimated to be ?6 >～ 3000 and ?⊥ ?4.