"Nanoscale zippers" in Gd5(SixGe(1-x))4: symmetry and chemical influences on the nanoscale zipping action

One critical parameter influencing the structural nature of the phase transitions in magnetocaloric materials Gd5(SixGe(1-x))4 is the Si/Ge ratio (x/1-x), because transition temperatures and structures depend crucially on this value. In this study, single-crystal X-ray diffraction indicates that Si and Ge atoms are neither completely ordered nor randomly mixed among the three crystallographic sites for these elements in these structures. Ge atoms enrich the T sites linking the characteristic slabs in these structures, while Si atoms enrich the T sites within them. Decomposition of the total energy into site and bond energy terms provides a rationale for the observed distribution, which can be explained by symmetry and electronegativity arguments. For any composition in Gd5(SixGe(1-x))4, a structure map is presented that will allow for a rapid assessment of the specific structure type.     

La-Fe-M(M=Al, Si)化合物磁热性能研究进展

介绍了La-Fe-M(M=AI,Si)化合物在磁热性能研究方面的最新进展。具有NaZn13型晶体结构,含高浓度Fe的La-Fe—M(M=AI,Si)化合物为良好的软磁材料;用少量的Co替代化合物中Si,Al元素可以将化合物的居里温度提高至室温;对La(Fe1-yCoy)xSi13-x化合物,适量的Si,Co组合可使化合物在室温产生可与Gd5Si2Ge2比拟的磁热效应;加入适量的间隙原子H,也可使La(FexSi1-x)13在室温的磁热性能远远大于金属Gd;对含Si量低及含Si量高的La(FexSi1-x)13化合物在相转变点附近由温度和磁场诱导相变的本质做了详细阐述。     

Gd5-xYxTt4 (Tt = Si or Ge): effect of metal substitution on structure, bonding, and magnetism

A crystallographic study and theoretical assessment of the Gd/Y site preferences in the Gd 5- x Y x Tt 4 ( Tt = Si, Ge) series prepared by high-temperature methods is presented. All structures for the Gd 5- x Y x Si 4 system belong to the orthorhombic, Gd 5Si 4-type (space group Pnma). For the Gd 5- x Y x Ge 4 system, phases with x < 3.6 and x >or= 4.4 adopt the orthorhombic, Sm 5Ge 4-type structure. For the composition range of 3.6 相似文献   

Electron-deficient Eu(6.5)Gd(0.5)Ge6 intermetallic: a layered intergrowth phase of the Gd5Si4- and FeB-type structures

A novel electron-poor Eu(6.5)Gd(0.5)Ge? compound adopts the Ca?Sn?-type structure (space group Pnma, Z = 4, a = 7.5943(5) ?, b = 22.905(1) ?, c = 8.3610(4) ?, and V = 1454.4(1) ?3). The compound can be seen as an intergrowth of the Gd?Si?-type (Pnma) R?Ge? (R = rare earth) and FeB-type (Pnma) RGe compounds. The phase analysis suggests that the Eu(7-x)Gd(x)Ge? series displays a narrow homogneity range of stabilizing the Ca?Sn? structure at x ≈ 0.5. The structural results illustrate the structural rigidity of the 2(∝)[R?X?] slabs (X = p-element) and a possibility for discovering new intermetallics by combining the 2(∝)[R?X?] slabs with other symmetry-approximate building blocks. Electronic structure analysis suggests that the stability and composition of Eu(6.5)Gd(0.5)Ge? represents a compromise between the valence electron concentration, bonding, and existence of the neighboring EuGe and (Eu,Gd)?Ge? phases.     

Chemical pressure and rare-earth orbital contributions in mixed rare-earth silicides La(5-x)Y(x)Si4 (0 ≤ x ≤ 5)

A crystallographic study and theoretical analysis of the structural and La/Y site preferences in the La(5-x)Y(x)Si(4) (0 ≤ x ≤ 5) series prepared by high-temperature methods is presented. At room temperature, La-rich La(5-x)Y(x)Si(4) phases with x ≤ 3.0 exhibit the tetragonal Zr(5)Si(4)-type structure (space group P4(1)2(1)2, Z = 4, Pearson symbol tP36), which contains only Si-Si dimers. On the other hand, Y-rich phases with x = 4.0 and 4.5 adopt the orthorhombic Gd(5)Si(4)-type structure (space group Pnma, Z = 4, Pearson symbol oP36), also with Si-Si dimers, whereas Y(5)Si(4) forms the monoclinic Gd(5)Si(2)Ge(2) structure (space group P2(1)/c, Z = 4, Pearson symbol mP36), which exhibits 50% "broken" Si-Si dimers. Local and long-range structural relationships among the tetragonal, orthorhombic, and monoclinic structures are discussed. Refinements from single crystal X-ray diffraction studies of the three independent sites for La or Y atoms in the asymmetric unit reveal partial mixing of these elements, with clearly different preferences for these two elements. First-principles electronic structure calculations, used to investigate the La/Y site preferences and structural trends in the La(5-x)Y(x)Si(4) series, indicate that long- and short-range structural features are controlled largely by atomic sizes. La 5d and Y 4d orbitals, however, generate distinct, yet subtle effects on the electronic density of states curves, and influence characteristics of Si-Si bonding in these phases.     

Polygallide RE2MGa9Ge2 (RE = Ce, Sm; M = Ni, Co) phases grown in molten gallium

The quaternary intermetallics Ce2CoGa9Ge2, Ce2NiGa9Ge2, and Sm2NiGa9Ge2 were prepared by reacting elemental metals in excess of gallium at 850 degrees C. The title compounds crystallize in the tetragonal space group P4/nmm in the Sm2Ni(Si(1-x)Ni(x))Al4Si6 structure type with cell parameters a = 5.9582(5) A, c = 15.0137(18) A, and a = 5.9082(17) A, c = 14.919(6) A, Z = 2, for Ce2CoGa9Ge2 and Sm2NiGa9Ge2, respectively. The structures are composed of covalently bonded three-dimensional networks of [CoGa9Ge2] in which the rare-earth metals fill the voids forming a 2D square net. The structures of RE2MGa9Ge2 are Ga-rich and possess extensive Ga-Ga bonding even though the Ga atoms do not form a network on their own. Magnetic susceptibility measurements for Ce2CoGa9Ge2 and Ce2NiGa9Ge2 show Curie-Weiss paramagnetism, consistent with presence of Ce(3+) ions. Magnetocrystalline anisotropy was observed for Ce2NiGa9Ge2, with the magnetically easy axis lying along the [001] crystallographic direction. A transition to an antiferromagnetic state was observed below 4 K in the easy direction of magnetization. In the magnetically hard direction of the basal plane, paramagnetic behavior was observed down to 1.8 K.     

Structure and properties of Gd3Ge4: the orthorhombic RE3Ge4 structures revisited (RE = Y, Tb-Tm)

The new binary compound Gd(3)Ge(4) has been synthesized and its structure has been determined from single-crystal X-ray diffraction. Gd(3)Ge(4) crystallizes in the orthorhombic space group Cmcm (No. 63) with unit cell parameters a = 4.0953(11) A, b = 10.735(3) A, c = 14.335(4) A, and Z = 4. Its structure can be described as corrugated layers of germanium atoms with gadolinium atoms enclosed between them. The bonding arrangement in Gd(3)Ge(4) can also be derived from that of the known compound GdGe (CrB type) through cleavage of the (infinity)(1)[Ge(2)] zigzag chains in GdGe and a subsequent insertion of an extra germanium atom between the resulting triangular fragments. Formally, these characteristics represent isotypism with the Er(3)Ge(4) type (Pearson's oC28). However, re-examination of the crystallography in the whole RE(3)Ge(4) series (RE = Y, Tb-Tm) revealed discrepancies and called into question the accuracy of the originally determined structures. This necessitated a new rationalization of the bonding, which is provided in the context of a comparative discussion concerning both the original and revised structure models, along with an analysis of the trends across the series. The temperature dependence of the magnetic susceptibility of Gd(3)Ge(4) shows that it is paramagnetic at room temperature and undergoes antiferromagnetic ordering below 29 K. Magnetization, resistivity, and calorimetry data for several other members of the RE(3)Ge(4) family are presented as well.     

Structure and physical properties of ternary rare-earth cobalt bismuth intermetallics (RE)12Co5Bi (RE = Y, Gd, Tb, Dy, Ho, Er, Tm)

The rare-earth intermetallic compounds (RE)12Co5Bi (RE = Y, Gd, Tb, Dy, Ho, Er, Tm) were prepared by arc-melting and annealing at 600 degrees C. These compounds extend the previously known (RE)6M2+xX1-x (M = Co, Ni; X = Ga, In, Sn, Pb) series with the Ho6Co2Ga-type structure to X = Bi. The crystal structure of Ho12Co5Bi was refined by the Rietveld method from powder X-ray diffraction data obtained using synchrotron radiation (Pearson symbol oI36, orthorhombic, space group Immm, Z = 2, a = 9.37598(14) A, b = 9.37871(14) A, c = 9.85465(13) A). Unlike other Ho6Co2Ga-type compounds, the 2a site in Ho12Co5Bi is exclusively occupied by Co atoms. Four-probe electrical resistivity measurements on sintered polycrystalline samples of (RE)12Co5Bi indicated metallic behavior. Magnetic measurements revealed behavior ranging from frequency-dependent maxima in the ac susceptibility for Y12Co5Bi to possible ferrimagnetic ordering for Gd12Co5Bi to antiferromagnetic ordering with metamagnetic transitions for the remaining compounds. As confirmed by band structure calculations using Y12Co5Bi as a model compound, Y-Y and Y-Co interactions are the most important bonding components, but matrix effects are likely responsible for anomalously short Co-Co contacts in the structure.     

The formal combination of three singlet biradicaloid entities to a singlet hexaradicaloid metalloid Ge14[Si(SiMe3)3]5[Li(THF)2]3 cluster

The reaction of GeBr with LiSi(SiMe(3))(3) leads to the metalloid cluster compound [(THF)(2)Li](3)Ge(14)[Si(SiMe(3))(3)](5) (1). After the introduction of a first cluster of this type, in which 14 germanium atoms form an empty polyhedron, [(THF)(2)Li](3)Ge(14)[Ge(SiMe(3))(3)](5) (2), we present here further investigations on 1 to obtain preliminary insight into its chemical and bonding properties. The molecular structure of 1 is determined via X-ray crystal structure solution using synchrotron radiation. The electronic structure of the Ge(14) polyhedron is further examined by quantum chemical calculations, which indicate that three singlet biradicaloid entities formally combine to yield the singlet hexaradicaloid character of 1. Moreover, the initial reactions of 1 after elimination of the [Li(THF)(2)](+) groups by chelating ligands (e.g., TMEDA or 12-crown-4) are presented. Collision induced dissociation experiments in the gas phase, employing FT-ICR mass spectrometry, lead to the elimination of the singlet biradicaloid Ge(5)H(2)[Si(SiMe(3))(3)](2) cluster. The unique multiradicaloid bonding character of the metalloid cluster 1 might be used as a model for reactions and properties in the field of surface science and nanotechnology.     

Intermetallic compounds with near Zintl phase behavior: RE2Zn3Ge6 (RE = La, Ce, Pr, Nd) grown from liquid indium

A series of compounds has been discovered while investigating reactions of rare earth, transition metals, and Ge in excess indium. These compounds, RE2Zn3Ge6 (RE = La, Ce, Pr, Nd), are isostructural, crystallizing in the orthorhombic space group Cmcm with lattice parameters a = 5.9691(9) angstroms, b = 24.987(4) angstroms, and c = 5.9575(9) angstroms for La2Zn3Ge6, a = 5.9503(5) angstroms, b = 24.761(2) angstroms, and c = 5.9477(5) angstroms for the Ce analogue, a =5.938(2) angstroms, b = 24.708(8) angstroms, and c = 5.936(2) angstroms for Pr2Zn3Ge6, and a = 5.9094(7) angstroms, b = 24.619(3) angstroms, and c = 5.9063(5) angstroms for the Nd analogue. The structure is composed of PbO-like ZnGe layers and ZnGe4 cage layers and is related to the Ce4Zn8Ge(11-x) structure type. The bonding in the system can be rationalized using the Zintl concept resulting in a material that is expected to be a valence precise semiconductor, although its behavior is more consistent with it being a semimetal, making it an intermediate case. The results of band structure calculations and magnetic measurements of these compounds are discussed.     

Crystal structure, coloring problem and magnetism of Gd(5-x)Zr(x)Si4

Ternary Gd(5-x)Zr(x)Si(4) silicides were synthesized by arc melting of the constituent elements and subsequent heat treatments. The Gd(5-x)Zr(x)Si(4) phases adopt the orthorhombic Gd(5)Si(4)-type (space group Pnma) structure for x≤ 0.25 and the tetragonal Zr(5)Si(4)-type (space group P4(1)2(1)2) structure for x≥ 1.0, respectively. The samples with intermediate compositions contain two phases. Single-crystal X-ray diffraction reveals a preferential site occupancy for Zr on the three metal sites in the order of M3 > M2 > M1. Size arguments based on the local coordination environments suggest that the larger Gd atoms preferentially occupy the larger M1 site, while the smaller Zr atoms tend to occupy the smaller metal sites, M2 and M3. Tight-binding linear-muffin-tin orbital calculations illustrate a role of the metal-silicon bonds in the metal site occupation. An increase in the valence electron concentration through the Zr substitution weakens the Si-Si interactions but enhances the metal-silicon and metal-metal interactions. The Curie temperature of Gd(5-x)Zr(x)Si(4) decreases gradually with the increasing Zr content.     

RE(AuAl2)nAl2(AuxSi1-x)2: a new homologous series of quaternary intermetallics grown from aluminum flux

The combination of early rare earth metals (La- to Gd and Yb), gold, and silicon in molten aluminum results in the formation of intermetallic compounds with four related structures, forming a new homologous series: RE[AuAl2]nAl2(AuxSi(1-x))2, with x approximately 0.5 for most of the compound and n = 0, 1, 2, and 3. Because of the highly reducing nature of the Al flux, rare earth oxides instead of metals can also be used in these reactions. These compounds grow as large plate-like crystals and have tetragonal structure types that can be viewed as intergrowths of the BaAl4 structure and antifluorite-type AuAl2 layers. REAuAl2Si materials form with the BaAl4 structure type in space group I4/mmm (cell parameters for the La analogue are a = 4.322(2) A, c = 10.750(4) A, and Z = 2). REAu2Al4Si forms in a new ordered superstructure of the KCu4S3 structure type, with space group P4/nmm and cell parameters of the La analogue of a = 6.0973(6) A, c = 8.206(1) A, and Z = 2. REAu3Al6Si forms in a new I4/mmm symmetry structure type with cell parameters of a = 4.2733(7) A, c = 22.582(5) A, and Z = 2 for RE = Eu. The end member of the series, REAu4Al8Si, forms in space group P4/mmm with cell parameters for the Yb analogue of a = 4.2294(4) A, c = 14.422(2) A, and Z = 1. New intergrowth structures containing two different kinds of AuAl2 layers were also observed. The magnetic behavior of all these compounds is derived from the RE ions. Comparison of the susceptibility data for the europium compounds indicates a switch from 3-D magnetic interactions to 2-D interactions as the size of the AuAl2 layer increases. The Yb ions in YbAu(2.91)Al(6)Si(1.09) and YbAu(3.86)Al(8)Si(1.14) are divalent at high temperatures.     

Hydrothermal growth and structural studies of Si(1-x)Ge(x)O2 single crystals

The substitution of germanium in the α-quartz structure is a method investigated to improve the piezoelectric properties and the thermal stability of α-quartz. Growth of α-quartz type Si(1-x)Ge(x)O(2) single crystals was performed using a temperature gradient hydrothermal method under different experimental conditions (pressure, temperature, nature of the solvent, and the nutrient). To avoid the difference of dissolution kinetics between pure SiO(2) and pure GeO(2), single phases Si(1-x)Ge(x)O(2) solid solutions were prepared and used as nutrients. The influence of the nature (cristobalite-type, glass) and the composition of this nutrient were also studied. Single crystals were grown in aqueous NaOH (0.2-1 M) solutions and in pure water. A wide range of pressures (95-280 MPa) and temperatures (315-505 °C) was investigated. Structures of single crystals with x = 0.07, 0.1, and 0.13 were refined, and it was shown that the structural distortion (i.e., θ and δ) increases with the atomic fraction of Ge in an almost linear way. Thus, the piezoelectric properties of Si(1-x)Ge(x)O(2) solid solution should increase with x, and this material could be a good candidate for technological applications requiring a high piezoelectric coupling factor or high thermal stability.     

Decoupling the electrical conductivity and Seebeck coefficient in the RE2SbO2 compounds through local structural perturbations

Compromise between the electrical conductivity and Seebeck coefficient limits the efficiency of chemical doping in the thermoelectric research. An alternative strategy, involving the control of a local crystal structure, is demonstrated to improve the thermoelectric performance in the RE(2)SbO(2) system. The RE(2)SbO(2) phases, adopting a disordered anti-ThCr(2)Si(2)-type structure (I4/mmm), were prepared for RE = La, Nd, Sm, Gd, Ho, and Er. By traversing the rare earth series, the lattice parameters of the RE(2)SbO(2) phases are gradually reduced, thus increasing chemical pressure on the Sb environment. As the Sb displacements are perturbed, different charge carrier activation mechanisms dominate the transport properties of these compounds. As a result, the electrical conductivity and Seebeck coefficient are improved simultaneously, while the number of charge carriers in the series remains constant.     

Electrodeposition of Ge, Si and Si x Ge 1-x from an air- and water-stable ionic liquid

The electrodeposition of Ge, Si and, for the first time, of Si(x)Ge(1-x) from the air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py(1,4)]Tf(2)N) containing GeCl(4) and/or SiCl(4) as precursors is investigated by cyclic voltammetry and high-resolution scanning electron microscopy. GeCl(2) in [Py(1,4)]Tf(2)N is electrochemically prepared in a two-compartment cell to be used as Ge precursor instead of GeCl(4) in order to avoid the chemical attack of Ge(iv) on deposited Ge. Silicon, germanium and Si(x)Ge(1-x) can be deposited reproducibly and easily in this ionic liquid. Interestingly, the Si(x)Ge(1-x) deposit showed a strong colour change (from red to blue) at room temperature during electrodeposition, which is likely to be due to a quantum size effect. The observed colours are indicative of band gaps between at least 1.5 and 3.2 eV. The potential of ionic liquids in Si(x)Ge(1-x) electrodeposition is demonstrated.     

Energetics and thermodynamic stability of the mixed valence ytterbium germanides

The results of an experimental study concerning the thermodynamic stability of the Yb germanides, described as intermediate valence compounds, complemented by a computational investigation for the Yb3Ge5 compound are reported. These compounds belong to the rare earth (RE) tetrelides (tetrel = Si, Ge, i.e., group 14 elements), a class of intermetallic materials showing unusual and promising physical properties (giant magnetocaloric effect, magnetostriction, and magnetoresistence). The high-temperature decomposition reactions of the Yb-Ge intermediate phases were studied experimentally by means of the KEMS (Knudsen effusion mass spectrometry) and KEWL (Knudsen effusion weight loss) techniques. From the reaction enthalpies derived by measuring the Yb(g) decomposition pressures as a function of temperature, the heats of formation of five out of six of the intermediate phases in the Yb-Ge system were calculated. From the computational side, the stability of the Yb3Ge5(s) compound has been investigated by DFT-LCAO-B3LYP (density functional theory-linear combination of atomic orbitals-hybrid b3lyp exchange-correlation functional) first principles calculations deriving its equilibrium geometry and the enthalpy of formation at 0 K in relation to the intermediate valence state of Yb in the lattice.     

Higher manganese silicide nanowires of Nowotny chimney ladder phase

We report the synthesis, structural identification, and electrical properties of the first one-dimensional (1-D) nanomaterials of a semiconducting higher manganese silicide (MnSi(2-x)) with widths down to 10 nm via chemical vapor deposition of the single-source precursor Mn(CO)(5)SiCl(3). The complex Nowotny chimney ladder structure of these homologous higher manganese silicides, also referred to as Mn(n)Si(2n-m), MnSi(1.75), or MnSi(1.8), contributes to the excellent thermoelectric performance of the bulk materials, which would be enhanced by phonon scattering due to 1-D nanoscale geometry. The morphology, structure, and composition of MnSi(2-x) nanowires and nanoribbons are examined using electron microscopy and X-ray spectroscopy. Elaborate select area electron diffraction analysis on single-crystal nanowires reveals the phase to be Mn(19)Si(33), one of a series of crystallographically distinct higher manganese silicides that have a Nowotny chimney ladder structure. Electrical transport study of single nanowires shows that they are degenerately doped with a low resistivity (17 mohms x cm) similar to the bulk.     

杂硼原子簇XB6+ (X=C,Si, Ge,Sn, Pb)的稳定性和芳香性

利用从头算MP2方法和密度泛函理论B3LYP和B3PW91方法, 研究了杂硼原子簇XB₆⁺ (X=C, Si, Ge, Sn, Pb)的结构、稳定性及化学键合情况. 对C, Si, Ge, B使用6-311+G(d)基组, 对Sn和Pb使用LANL2DZ赝势基组. 研究结果表明, 具有C_s对称性的假平面XB₆⁺ (X=C, Si, Ge, Sn, Pb)结构是势能面上的全域极小点, 其稳定性要高于C_6v对称性的锥形结构和C₂对称性的假锥形结构. 在B3LYP水平上, 对这些异构体的势能面的极小点进行了自然键轨道(NBO)的分析; 对最稳定构型的最高占据分子轨道(HOMO)和最低空轨道(LUMO)能级差、分子轨道(MO)和核独立化学位移(NICS)进行了计算和讨论. 分析了杂原子和硼原子间、相邻硼原子间的键合情况, 讨论了最稳定构型的芳香性质.     

平面五配位硅、 锗XBe5H6(X=Si,Ge)团簇

采用密度泛函理论PBE0方法, 在aug-cc-pVTZ水平上理论预测了含平面五配位硅和锗原子的XBe₅H₆ (X=Si, Ge)团簇. 势能面系统搜索及高精度量化计算表明, 它们均为全局极小结构. XBe₅H₆(X=Si, Ge)团簇整体呈完美的扇形结构: Si/Ge原子被5个金属Be原子配位; 4个H原子以桥基方式与Be原子相键连, 剩余的2个 H原子以端基方式与两端的Be原子成键. 化学键分析表明, XBe₅H₆(X=Si, Ge) 团簇中XBe₅单元具有完全离域的1个π及3个σ键, 外围铍氢间形成4个Be—H—Be 三中心二电子(3c-2e)键及2个定域的Be—H键. XBe₅单元上离域的2π及6σ电子赋予体系π和σ双重芳香性, 并使Si/Ge原子满足八隅律（或八电子规则）. 能量分解-化学价自然轨道分析揭示, Si/Ge和Be₅H₆之间主要为电子共享键.