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).     

An ESR study of phase transitions in crystals of M(BF4)2·6H2O (M = Fe,Co, Ni,Zn)

From a temperature dependent ESR study of Mn²⁺-doped crystals of M(BF₄)₂·6H₂O, M Zn, Co and Ni, new structural phase transitions have been detected and studied. First order structural phase transitions occur in Co(BF₄)₂·6H₂O at T₁ ~ 281K, T₂~189 K and T₃~172K (during cooling), in Zn(BF₄)₂·6H₂O at T₁ ~ 286 K and in Ni(BF₄)₂·6H₂O at T₁ ~ 301 K. A continuous phase transition occurs in Co(BF₄)₂·6H₂O at T_p ~ 257 K, in Zn(BF₄)₂·6H₂O at T_p ~ 277 K and in Ni(BF₄)₂·6H₂O at T_p ~ 294 K. The ESR spectral characteristics suggest similarities in the structures of these fluoroborate compounds in the phase above T₁ with the room temperature structure of Mg(ClO₄)₂·6H₂O. All these compounds are found to have a tendency to crystallise in a triply-twinned pseudo-hexagonal form, although the unit cell above T₁ is found to be orthorhombic. The structural changes related to the water octahedron around the metal at T₁ were found to be very small and basically the same for these three compounds. Although the unit cell structure of Fe(BF₄)₂·6H₂O above the first order phase transition temperature T₁ was found to be similar to that of the other fluoroborate compounds, the structural changes occurring at T₁ appeared to be quite different. The low temperature thermal behaviour differs considerably in the Co, Fe and Zn compounds.     

Systematics of Mössbauer parameters in Fe57-doped titanate and germanate ilmenites

The Mössbauer spectra of ilmenite (FeTiO₃), Fe²⁺-doped ilmenites, MTiO₃ (M = Cd, Mn, Zn, Co, Mg and Ni) and MGeO₃ (M = Mn, Zn and Mg), have been studied from 4.2 K to room temperature. Systematic variations in the isomer shift and quadrupole splitting at room temperature are correlated with the change in ionic radii of the host M ions and the c/a ratio of the host crystal, respectively. The quadrupole splittings show a remarkable temperature variation; the magnetic ilmenites show either a sudden increase or a sudden decrease of quadrupole splittings below the Néel temperature, depending on the orientation of the spin axis with respect to the c axis.     

Vibrational Spectroscopic Studies of 3,4-Lutidine Metal (II) Tetracyanonickelate Complexes

Infrared and Raman spectra of seven new metal (II) 3,4-lutidine tetracyanonickelate complexes, M(3,4 L)₂ Ni(CN)₄ [where 3,4 L = 3,4 - dimethyl-pyridine or 3,4-lutidine; M = Mn, Fe, Co, Zn, Ni, Cu or Cd] (abbreviated to M - Ni - 3,4 L) have been investigated. Spectroscopic and magnetic susceptibility measurements indicate that the compounds have the structure of Hofmann-type complexes. The copper complex has spectral features different from the other compounds.     

metamagnetic behavior of linear chain pyridine compounds: Co(Pyridine)2Cl2, Fe(Pyridine)2Cl2, Fe(Pyridine)2(NCS)2 and Ni(Pyridine)2Cl2

Magnetic phase transitions in the pyridine (pyr) compounds Co(pyr)₂Cl₂, Fe(pyr)₂Cl₂, Fe(pyr)₂(NCS)₂ and Ni(pyr)₂Cl₂ have been observed at applied magnetic fields of ～0.7, 0.7, 1.1 and 2.7 kG respectively. These low field phase transitions are observed in the Fe and Ni compounds at T = 4.2 K, and in the Co compound at T < 3K, and are consistent with metamagnetic behavior. Magnetic saturation is not achieved in any of these compounds for fields of 60 kG, reflecting high anisotropy.     

Investigation of the EPR parameters and local structures for Cu2+ in Bis(l-asparaginato) M(II) catalysts (M=Zn,Cd, Mg)

The electron paramagnetic resonance (EPR) parameters (g factors and hyperfine structure constants) for Cu²⁺ in Bis(l-asparaginato) M(II) catalysts (M=Zn, Cd, Mg) are theoretically investigated using the high order perturbation formulas of these parameters for 3d⁹ ions in orthorhombically elongated octahedra. Ligand orbital and spin–orbit coupling contributions are included from the cluster approach in view of strong covalency. The ligand octahedra (i.e., [CuO₄N₂]^12? clusters) are found to experience axial and perpendicular local bond length variations Δ (≈0.19–0.25 Å) and δ (≈0.12–0.14 Å) due to the Jahn–Teller effect and size mismatch, which are dissimilar to those of host M²⁺ sites in pure compounds. The theoretical EPR parameters based on the above local structures show good agreement with the observed values, and some improvements are achieved as compared with those in the previous work. The local structures of these centers are discussed.     

Magnetic,electrical and structural properties of some ternary and quaternary spinels with chromium

Spinel compounds with the general formulas ACr₂X₄ and ACr_2−xB_xX₄ (where A=Cd, Zn, Hg, Ga, Cu; X=S, Se, Te, O; B=Ga, In, Sb), including also substitution of two different cations in the tetrahedral subarray, exhibit different correlations of the magnetic and electrical properties. These properties are correlated with the ionic radii of cations and anions. The solid solutions of the boundary compounds reveal, e.g. correlations of metallic conductivity and a semiconductor–metal phase transition. In some spinel solid solutions the latter phase transition is accompanied by the magnetic phase transitions, i.e. either AF-F or Fi-F. Magnetic and electrical properties and their correlations in different spinel series with chromium are discussed in the frames of the phase diagram of the spinel-type compounds with chromium. Different mechanisms leading to the spin-glass state are discussed and illustrated.     

Preparation,Chemical Characterization and Electronic Spectra of 6-(2-Pyridylazo)-3-Acetamidophenol and Its Metal Complexes

The stereochemistry of new iron (III), cobalt (II), nickel (II), copper (II), zinc (II) and cadmium (II) complexes of 6-(2-pyridylazo)-3-acetamidophenol (H2L) was studied on the basis of their analytical, spectroscopic, magnetic and conductance data. the dissociation constant of the ligand, as well as the stability constants of its metal complexes had been determined by spectrophotometric method. on the basis of infrared spectra, the coordination behaviour of the ligand to the metal ions was investigated. Magnetic susceptibility and solid reflectance spectra measurements were used to infer the structure. the isolated complexes were found to have the general formulae [M (HL). xH₂O] (A).yH₂O, M = Cu (II), Zn (II), Cd (II) and Fe (HI); HL = 6-(2-pyridylazo)-3-acetamido-phenol; a = acetate in the case of Cu (II) and Zn (II) or chloride in the case of Cd (II) and Fe (Ill), x = 1-3 and y=0-5. for [M (H₂L).xH₂O]Cl₂.yH₂O, M = Ni (II) and Co (II); HL = 6-(2-pyridyl-azo)-3-acetamidophenol, x=3 and y=5-6).     

重电子金属CeCu5.8M0.2（M=Ni,Zn, Cd）低温物性的比较

研究了不同元素等量掺杂下重电子金属CeCu_5.8M_0.2(M=Ni，Zn，Cd)低温电阻、比热容和磁化率随温度的变化关系.分析讨论了掺杂元素M(M=Ni，Zn，Cd)的磁性、价态及原子尺寸对近藤温度T_K、相干温度（即电阻极大值的温度Ｔ^R_max）、每个Ce离子在较高温度时的平均磁矩μ_Ｂ以及在温度降低时被传导电子自旋屏蔽过程的影响. 关键词： 重电子系统 低温电阻 低温比热容 磁化率     

Dielectric and acoustic properties of the family of new lead-free materials with the general formula BiMe 2/3Sb1/3O3 (Me = Mg, Ni, Co, Zn)

A family of new lead-free materials with the general formula BiMe _2/3Sb_1/3O₃ (Me = Mg, Ni, Co, Zn) have been synthesized using the standard ceramic technology. The temperature dependences of the permittivity ??? have been studied at frequencies from 0.5 to 1000 kHz in the temperature range from 300 to 800 K. At high temperatures, the permittivity ??? of the Ni-, Mg-, Co-, and Zn-containing materials has been found to exhibit maxima (at 765, 768, 748, and 780 K, respectively) related to structural phase transitions, which has been confirmed by the measurements of the elastic, inelastic, and thermal properties.     

One-pot low temperature synthesis of MFe2O4 (M=Co,Ni, Zn) superparamagnetic nanocrystals

Magnetic MFe₂O₄ (M=Co, Ni, Zn) nanocrystals with a diameter about 30 nm and a nearly spherical shape were synthesized via a simple hydrothermal approach. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy have been used to investigate the as-prepared magnetic MFe₂O₄ (M=Co, Ni, Zn) nanocrystals. Magnetic properties of the as-prepared samples have been detected by a vibrating sample magnetometer at room temperature and the results show that the as-prepared magnetic MFe₂O₄ nanocrystals are a type characteristic of superparamagnetic materials. These superparamagnetic nanocrystals are believed to be promising for wide engineering applications, such as drug delivery, bioseparation, and magnetic resonance imaging.     

Mössbauer study of Mg–Ni(Fe) alloys processed as materials for solid state hydrogen storage

Mg–Ni–Fe magnesium-rich intermetallic compounds were prepared following two distinct routes. A Mg₈₈Ni₁₁Fe₁ sample (A) was prepared by melt spinning Mg–Ni–Fe pellets and then by high-energy ball milling for 6 h the obtained ribbons. A (MgH₂)₈₈Ni₁₁Fe₁ sample (B) was obtained by high-energy ball milling for 20 h a mixture of Ni, Fe and MgH₂ powders in the due proportions. A SPEX8000 shaker mill with a 10:1 ball to powder ratio was used for milling in argon atmosphere. The samples were submitted to repeated hydrogen absorption/desorption cycles in a Sievert type gas–solid reaction controller at temperatures in the range 520?÷?590 K and a maximum pressure of 2.5 MPa during absorption. The samples were analysed before and after the hydrogen absorption/desorption cycles by X-ray diffraction and Mössbauer spectroscopy. The results concerning the hydrogen storage properties of the studied compounds are discussed in connection with the micro-structural characteristics found by means of the used analytical techniques. The improved kinetics of hydrogen desorption for sample A, in comparison to sample B, has been ascribed to the different behaviour of iron atoms in the two cases, as proved by Mössbauer spectroscopy. In fact, iron results homogeneously distributed in sample A, partly at the Mg₂Ni grain boundaries, with catalytic effect on the gas–solid reaction; in sample B, instead, iron is dispersed inside the hydride powder as metallic iron or superparamagnetic iron.     

Structural Features of Phosphates Ca9 – xMxDy(PO4)7 (M = Zn2+ or Mg2+)

Physics of the Solid State - Phosphate solid solutions based on the whitlockite family Ca9&nbsp;–&nbsp;xMxDy(PO4)7 (M = Zn2+ or Mg2+) have been obtained. The samples have been...     

[M(SS)(NN)](M=Zn2+,Cd2+)配合物分子内跃迁与结构的关系

报道了配合物[M(SS)(NN)](M=Zn2 ,Cd2 )(SS=mnt2-,1,2-二氰基乙烯-1,2-二硫醇离子,NN=5-NO2-phen,5-硝基-1,10-邻菲咯啉)的合成,探讨了Zn(SS)(NN)和Cd(SS)(NN)在二甲基亚砜(DM-SO)、二甲基甲酰胺(DMF)、丙酮(acetone)、吡啶(Py)等溶剂中的电子吸收光谱。研究发现配合物的紫外区的吸收带270～280nm,320～350nm,350～390nm本质上属于配体mnt2-,5-NO2-phen内部的πb→π*跃迁,可见光区400～500nm本质上属于配体mnt2-到配体5-NO2-phen的荷移跃迁(LL′CT)。确认了标题配合物的荷移跃迁光谱在相关分子轨道能级图中的对应关系。标题配合物的LL′CT吸收带与组成相似配合物M(SS)(NN)(M=Co2 ,Fe2 ,Ni2 ,Cu2 )的对应吸收带相比较弱一些,这是由于[M(SS)(NN)](M=Zn2 ,Cd2 )的LL′CT谱带(7b2→7b1)是部分解除轨道禁阻的跃迁。     

Electronic structures of MRhO2, MRh2O4, RhMO4 and Rh2MO6 on the basis of X-ray spectroscopy and ESCA data

X-ray O Kα, Rh Mγ and a series of M Lα emission spectra, ESCA spectra of the valence and inner levels, and O K and Rh M_III quantum-yield spectra for X-ray photoemission of the rhodium double oxides MRhO₂ (M = Li, Na, K), MRh₂ O₄ (M = Be, Mg, Ca, Sr, Ba, Co, Ni, Cu, Zn, Cd, Pb), RhMO₄ (M = V, Nb, Ta) and Rh₂MO₆ (M = Mo, W) have been measured and the dependence of electronic structure on the metal M analysed. For all compounds the inner part of the valence band corresponds to O 2p_σ + O 2p_π + Rh 4d states, while the outer part corresponds to Rh 4d. The valence band is separated from the conduction band by a narrow gap of width less than 1 eV. The first empty band, near the bottom of the conduction band, is formed by Rh 4d states, followed by a band due to vacant O 2p states.     

The structural,electronic and magnetic properties of Ag4M and Ag4MCO (M = Sc–Zn) clusters

The structures, spectra and electronic and magnetic properties of Ag₄M and Ag₄MCO (M?=?Sc–Zn) clusters have been studied using density functional theory and CALYPSO structure searching method. Structural searches show that M atoms except Zn tend to occupy the highest coordination position in the ground state Ag₄M and Ag₄MCO clusters. Carbon monoxide is most easily adsorbed on Ag atom of Ag₄Zn and M atom of other Ag₄M. Infrared and Raman spectra, photoabsorption spectra and photoelectron spectra of Ag₄M and Ag₄MCO clusters are forecasted and can be used to identify these clusters from experiment. Analysis of electronic properties indicates that the adsorption of CO on Ag₄M clusters changes the zero vibrational energy (ZPVE) and increases stability of the host clusters. Dopant atoms except for Zn improve the stability of silver cluster. The Ag₄Ni cluster shows high chemical activity and maximum adsorption energy for carbon monoxide. Magnetism calculations reveal that the magnetic moment of Ag₄M (M?=?Mn–Ni) cluster adsorbed by carbon monoxide is decreased by 2 μ_B. The change of magnetic moment makes it possible to be used as a nanomaterial for carbon monoxide detection. Simultaneously, it is found that the adsorption of CO on Ag₄Cu cluster is a physical adsorption.     

Hume-Rothery electron concentration rule across a whole solid solution range in a series of gamma-brasses in Cu–Zn,Cu–Cd,Cu–Al,Cu–Ga,Ni–Zn and Co–Zn alloy systems

The aim of the present work is to examine if the Hume-Rothery stabilisation mechanism holds across whole solid solution ranges in a series of gamma-brasses with especial attention to the role of vacancies introduced into the large unit cell. The concentration dependence of the number of atoms in the unit cell, N, for gamma-brasses in the Cu–Zn, Cu–Cd, Cu–Al, Cu–Ga, Ni–Zn and Co–Zn alloy systems was determined by measuring the density and lattice constants at room temperature. The number of itinerant electrons in the unit cell, e/uc, is evaluated by taking a product of N and the number of itinerant electrons per atom, e/a, for the transition metal element deduced earlier from the full-potential linearised augmented plane wave (FLAPW)-Fourier analysis. The results are discussed within the rigid-band model using as a host the density of states (DOS) derived earlier from the FLAPW band calculations for the stoichiometric gamma-brasses Cu₅Zn₈, Cu₉Al₄ and TM₂Zn₁₁ (TM = Co and Ni). A solid solution range of gamma-brasses in Cu–Zn, Cu–Cd, Cu–Al, Cu–Ga and Ni–Zn alloy systems is found to fall inside the existing pseudogap at the Fermi level. This is taken as confirmation of the validity of the Hume-Rothery stability mechanism for a whole solute concentration range of these gamma-brasses. An exception to this behaviour was found in the Co–Zn gamma-brasses, where orbital hybridisation effects are claimed to play a crucial role in stabilisation.     

The investigations of phases with general formula M2FeV3O11, where M=Mg,Co, Ni,Zn by IR and Mössbauer spectroscopy

Phases of general formula M₂FeV₃O₁₁, where M=Mg, Co, Ni and Zn as well as the orthorhombic modification of FeNb₁₁O₂₉, have been investigated by the help of IR and Mössbauer spectroscopy. It was found that the isostructural compounds Co₂FeV₃O₁₁, Mg₂FeV₃O₁₁, Zn₂FeV₃O₁₁, as well as Ni₂FeV₃O₁₁ with a different structure have one single and almost identical chemical environment for iron(III). The large Mössbauer quadrupole splitting measured suggests that iron(III) is located in a highly distorted octahedron. The IR spectra of three isostructural M₂FeV₃O₁₁ compounds are similar but differ from that of Ni₂FeV₃O₁₁. The Mössbauer spectrum of orthorhombic FeNb₁₁O₂₉ has been fitted with two doublets, their hyperfine parameters indicating iron in distorted octahedral environment.     

Raman spectroscopy of M3B7O13X boracites (M = Cr,Co,Ni,Cu,Zn,Cd; X = Cl,Br,I)

We report results of a Raman study on single crystals of 16 boracites M₃B₇O₁₃X (M = Cr,Co,Ni,Cu,Zn,Cd; X = Cl,Br,I) over a broad temperature range. The Raman modes for all boracites in their high‐temperature prototype cubic (F3c) phase are compared. With decreasing temperature, most (but not all) compounds present a transition to the low‐temperature orthorhombic phase (Pca2₁) or to a sequence of orthorhombic, monoclinic (Pa), and trigonal (R3c) phases. The variations of the Raman spectra through different phases are studied in detail. Special attention is paid to the temperature hysteresis near the transitions and the dependence of transition temperature on the direction of crystal growth for the same material. Copyright © 2014 John Wiley & Sons, Ltd.     

Study of phase transitions in the system A1B11PO4 with A1 = Li,Rb and B11 = Mg,Ca, Sr,Ba, Zn,Cd, Pb

The series of the title compounds were prepared by solid-state reactions. The phase transitions between room temperature and 1450 °C were investigated by DTA and X-ray diffraction. All compounds undergo at least one reversible phase transition in the solid state. The Rb containing compounds, with the exception of those with Cd and Zn, show no liquid phase up to 1450 °C. The phases formed crystallize with various structures which can be described partly as distorted olivine, LiKSO₄, CsZnPO₄ or glaserite. RbCdPO₄ shows an incommensurate structure with a one-dimensional modulation.