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1.
The magnetic properties of a series of cubic perovskite materials, Eu(Al0.5Ta0.5)O3, Eu(Mg0.5W0.5)O3, and Eu(Lu0.5Ta0.5)O3 have been investigated using bulk magnetic and Mössbauer techniques. Eu(Al0.5Ta0.5)O3 is a ferromagnet (Tc ~ 5°K, θc = + 8°K), Eu(Lu0.5Ta0.5)O3 is an antiferromagnet (TN = 4.0, θc = ?8°K), while Eu(Mg0.5W0.5)O3 is probably antiferromagnetic (TN = 2.8°K, θc = ? 1°K). These data are compared with the known properties of EuLiH3 and EuTiO3 and a sharp drop in θc as a function of increasing lattice constant is noted. A molecular field theory analysis of the data yields two possible sets of nn (J1) and nnn (J2) exchange constants for each compound which are compared with existing theories.  相似文献   

2.
The hydrogenation properties of the LaNi5 (CaCu5 type, hP6, P6/mmm) and Pd substituted derivatives LaNi5−xPdx compounds have been studied in the whole homogeneity range of the solid solution (0.25≤x≤1.5). The pressure versus hydrogen content isotherms show several plateaus and an increase of the plateau pressure as a function of palladium concentration. The volume increase of the Pd substituted alloys should have resulted in a lowering, and not an increase, of the plateau pressure, according to the conventional models based on the size effect. In order to elucidate the origin of this anomalous behavior, both an experimental and a theoretical ab initio electronic structure investigation have been carried out. Experimentally, the nature and the structural properties of the hydrides have been studied by both in situ and ex situ neutron diffraction. The crystal structures of the three hydride phases are reported (LaNi3.5Pd1.5D1.96, filled-up CaCu5 type, P6/mmm; LaNi4PdD2.72, LaNi2(Ni0.75Pt0.25)3H2.61 type, oI128, Ibam; LaNi4.75Pd0.25D5.67, partly ordered CaCu5 type, P6mm). In addition, the phase diagram of LaNi5−xPdx-H system has been investigated. The electronic and thermodynamic properties of both intermetallic compounds and the hydrides have been studied by ab initio electronic structure calculations. The theoretical results are in good agreement with our experimental data, and show that electronic interactions play a major role in the hydrogenation behavior of these Pd substituted intermetallic compounds, and that these effects cannot be accounted for by a simplistic model based on the size effect alone.  相似文献   

3.
Four novel compounds based on α-metatungstate [H2W12O40]6− (W12) and Ln-organic complexes, (NH4)4[Ln2(L)2(H2O)9(H2W12O40)]·nH2O (Ln=EuIII (1), GdIII (2), DyIII (4), n=11; TbIII (3), n=12; L=pyridine-3,5-dicarboxylate dianion) have been synthesized in aqueous solution and characterized by element analysis, IR spectrometry and thermogravimetric analysis. Single-crystal X-ray diffraction analyses reveal these compounds are isostructural with a P21/n space group. The W12 cluster acting as a tridentate ligand connects three Ln3+ ions, in turn, each Ln2 ion links two W12 clusters, as a result, a W12-Ln polymeric chain is formed. Coordination of pyridine-3,5-dicarboxylate ligands to the Ln3+ ions leads to a Ln-L polymeric chain. The two chains, W12-Ln and Ln-L, share Ln2 ions, resulting in a 2-D layer. Ring coordination of pyridine-3,5-dicarboxylate and W12 to the Ln ions changes some bond angles of W12 that leads to a slight distortion of W12 and splitting of vibration band of W-Oc-W. Solid-state photoluminescence properties of compounds 1−4 have been investigated.  相似文献   

4.
The K shell X-ray intensity ratios Kα2/Kα1, Kβ1,3/Kα1 and Kβ2/Kα1 for 21 elements with 65⩽Z⩽92 have been measured using an incident photon energy of 123.6 keV. The X-rays have been measured with a Si(Li) semiconductor detector. Kβ and Kα X-rays have been analyzed into the components Kβ1,3 and Kβ2 and Kα1 and Kα2, respectively, using a computer program. The experimental results were compared with the theoretical values of Scofield and available experimental results. All X-ray intensity ratios values have been plotted versus atomic number.  相似文献   

5.
Excess molar volumes VmE at 298.15 K were obtained, as a function of mole fraction x, for series I: {x1-C4H9Cl + (1 ? x)n-ClH2l + 2}, and II: {x1,4-C4H8Cl2 + (1 ? x)n-ClH2l + 2}, for l = 7, 10, and 14. 10, and 14. The instrument used was a vibrating-tube densimeter. For the same mixtures at the same temperature, a Picker flow calorimeter was used to measure excess molar heat capacities Cp, mE at constant pressure. VmE is positive for all mixtures in series I: at x = 0.5, VmE/(cm3 · mol?1) is 0.277 for l = 7, 0.388 for l = 10, and 0.411 for l = 14. For series II, VmE of {x1,4-C4H8Cl2 + (1 ? x)n-C7H16} is small and S-shaped, the maximum being situated at xmax = 0.178 with VmE(xmax)/(cm3 · mvl?1) = 0.095, and the minimum is at xmin = 0.772 with VmE(xmin)/(cm3 · mol?1) = ?0.087. The excess volumes of the other mixtures are all positive and fairly large: at x = 0.5, VmE/(cm3 · mol?1) is 0.458 for l = 10, and 0.771 for l = 14. The Cp, mEs of series I are all negative and |Cp, mE| increases with increasing l: at x = 0.5, Cp, mE/(J · K?1 · mol?1) is ?0.56 for l = 7, ?1.39 for l = 10, and ?3.12 for l = 14. Two minima are observed for Cp, mE of {x1,4-C4H8Cl2 + (1 ? x)n-C7H16}. The more prominent minimum is situated at xmin = 0.184 with Cp, mE(xmin)/(J · K?1 · mol?1) = ?0.62, and the less prominent at xmin = 0.703 with Cp, mE(xmin)/(J · K?1 · mol?1) = ?0.29. Each of the remaining two mixtures (l = 10 and 14) has a pronounced minimum at low mole fraction (xmin = 0.222 and 0.312, respectively) and a broad shoulder around x = 0.7.  相似文献   

6.
In a potentiometric titration of a solution that contains both the reduced form Red2 and the oxidized form Ox2 of a redox couple, at concentrations of c0Red2M and c0Ox2M, respectively, using as reagent a solution that contains the oxidized and reduced forms Ox1 and Red1 at concentrations of cOx1M and cRed1M, respectively, the reaction that occurs is nRed2 + n2Ox1 = n1Ox2 + n2Red1; Kt = exp[n1n2(E01′–E02′)/0.02569] if all of the reactants and products are monomeric and if the titration is done at 25°C. By applying weighted non-linear regression analysis to the data obtained in such a titration, if cOx1 is known, it is possible to evaluate four parameters: c0Red2, c0Ox2 , and the formal potentials E02′ and E01′ for the couple titrated and the reagent couple, respectively. For the common situation in which n1 and n2 are equal, this paper describes the ways in which the precisions of all four parameters depend, over a wide range of conditions, on their values and on the precisions of measurement of the volume of reagent and the potential of the indicator electrode.  相似文献   

7.
Bonding properties of sodium-cluster dimers, (X 4)2 and (X 8)2, whereX n is a jellium sphere corresponding to a cluster ofn atoms, were investigated by the linear-combination-of-jellium-orbitals method with local-spin-density-functional approximation. The stability ofn=8 clusters, observed in the experiment, is discussed in relation to the binding properties of dimers. We have found that (1) the (X 4)2 bonding has a covalent character, which makes theX 8 formation favorable, and (2)X 8 has an inert property because the force between jellium spheres in (X 8)2 is due to a weak dispersion force.  相似文献   

8.
The equilibrium geometries of Na n F n and Na n F n?1 are optimized forn=2, 3, 4 at the SCF level. The Na n F n molecules appear as formed by Na+ and F? ions. The paper studies the localization of the excess electron in the Na n F n?1 molecules. Na n F n?1 is obtained by removing from Na n F n a fluorine atom, and the excess electron takes the place of this lacking center, and allows a weak bond between the neighbouring Na atoms. Secondary minimum geometries, for which the excess electron has no defined place, are also studied.  相似文献   

9.
NMR measurements have been used to characterize the electron-beam (EB) induced polymerization of 1,6-hexanediol diacrylate. Hydrogen T1, T, and T2 values have been measured as a function of radiation dose. The T2 signal consists of a Gaussian component and a longer component consisting of two exponentials. The sum of the Gaussian and the short exponential intensities is strongly correlated with the polymer fraction determined by gel extraction. T2 values associated with the exponential component decrease rapidly with increasing dose. The T1 relaxation consists of two exponentials for low dose and a single exponential for high dose. The T relaxation consists of from two to three exponential components, and the departure from a single exponential decreases with increasing dose. T1 and T intensities are poorly correlated with gel extraction results. T1 and T minima occur at intermediate radiation dose, and T depends on H1 at high dose. Limited spin diffusion plays an important role in the T1 and T relaxation. Hydroquinone has little effect on the EB-induced polymerization.  相似文献   

10.
The structures of recently discovered new high-temperature modifications of cobalt molybdate, a′-and a″-CoMoO4, were determined. a′-and a″-CoMoO4 appear after the phase a-CoMoO4 is heated above the temperature range 700–1000°C. They seem to be the disordered modifications of a-CoMoO4 with metal atoms distributed at random in an a-CoMoO4 oxygen network.The F(hkl) values, calculated for variously disordered a-CoMoO4 structure, were compared with the observed intensities of diffraction lines changing in the course of aa′ and aa″ transitions. It was concluded that a″-CoMoO44 has a completely disordered structure with random distribution of both Co and Mo atoms in oxygen interatomic voids. The a′-CoMoO4 is a partly disordered modification, with random distribution of some cations only.The temperature and the kind of order-disorder transition depend on the method of preparation of a-CoMoO4 samples.The disordered modifications of cobalt molybdate may be supercooled—even to room temperature—before it transforms rapidly into low-temperature b-CoMoO4 form.  相似文献   

11.
The subsolidus phase relations of R2O3-CaO-CuO ternary systems (R=Nd, Sm, Gd, Tm) have been investigated by X-ray powder diffraction. All samples were synthesized at about 950° in air. There exists a ternary compound Ca14−xRxCu24O41 (x = 4 for R=Nd, Gd and x = 5 for R = Sm) and a ternary solid solution Ca2+xR2−xCu5O10 (R=Nd, Sm, Gd, Tm) with a wide composition range Δx of about 0.6. The compound Ca14−xRxCu24O41 possesses a layered orthorhombic structure and is isostructural to Sr14−xCaxCu24O41. The lattice parameters a and c of the compound are basically independent of the ionic radius of R, while the lattice parameter b and unit-cell volume V decrease substantially with the decrease of the ionic radii of R. The Ca2+xR2−xCu5O10 solid solution is isostructural to Ca2+xY2−xCu5O10, the structure of which is based on an orthorhombic “NaCuO2-type” subcell containing infinite one-dimensional chains of edge-shared square planar cuprate groups crosslinked by the layered cations Ca and R that locate in the inter-chain tunnels.  相似文献   

12.
王维 《高分子科学》2013,31(5):798-808
Crystal patterns in ultrathin films of six poly(ethylene oxide) fractions with molecular weights from 25000 to 932000 g/mol were characterized within crystallization temperature range from 20 ℃ to 60 ℃.Labyrinthine,dendritic and faceted crystal patterns were observed in different temperature ranges,and then labyrinthine-to-dendritic and dendritic-tofaceted transition temperatures T L-D and T D-F were quantitatively identified.Their molecular weight dependences are T L-D(M w) = T L-D(∞) K L-D /M w,where T L-D(∞) = 38.2 ℃ and K L-D = 253000 ℃.g/mol and T D-F(M w) = T D-F(∞) K D-F /M w,where T D-F(∞) = 54.7 ℃ and K D-F = 27000 ℃.g/mol.Quasi two-dimensional blob models were proposed to provide empirical explanations of the molecular weight dependences.The labyrinthine-to-dendritic transition is attributed to a molecular diffusion process change from a local-diffusion to diffusion-limited-aggregation(DLA) and a polymer chain with M w ≈ 253000 g/mol within a blob can join crystals independently.The dendritic-to-faceted transition is attributed to a turnover of the pattern formation mechanism from DLA to crystallization control,and a polymer chain with a M w ≈ 27000 g/mol as an independent blob crosses to a depletion zone to join crystals.These molecular weight dependences reveal a macromolecular effect on the crystal pattern formation and selection of crystalline polymers.  相似文献   

13.
Our preparation of Ti(h5?C5H5)2 S5 by the reaction of elemental sulfur with Ti(h5?C5H5)2(CO)2 in hexane and of V(h5?C5H5)2S5?12 H2O by the reacti of V(h5?C5H5)2 Cl2 with Na2S5 in THF and structural analyses by single crystal X-ray diffraction (together with infrared, solution EPR, and temperaturedependent magnetic susceptibility measurements) represent an extension of our previous work on M(h5?C5H5)2 (SC6H5)2 (M = Ti, V). The crystallographic results provide further support of our previous conclusions that the Ballhausen—Dahl model is not valid for M(h5?C5H5)2L2 systems. The structuralfeatures of the chair-like titanium and vanadium pentasulfide molecules are compared to the corresponding phenylmercapto analogs and to the chair-like cyclohexasulfur molecule in rhombohedral sulfur. Ti(h5?C5H5)2S5 was isolated as a mixture of monoclinic and orthorhombic Crystalline phases-which were both characterized by preliminary X-ray data. A complete Structural determination and refinement of the monoclinic phase, which contains two independent molecules in a cell of dimensions a 22.843(2), b 7.958(1), c 14.465(1) Å, β 90.074(4)° and symmetry P21/c, yielded R1 5.3 % and R2 5.9 % for 2168 independent diffractometry-collected data with I≥ 2.5o(I). V(h5?C5H5)2S5-12 H2O contains four V(h5?C5H5)2S5 molecules and two water molecules of hydration (of crystallographic site symmetry C2-2) in onorthorhombic unit cell of symmetry P21212 and of dimensions a 13.491(1), b 12.748(1), c 7.715(1) Å. Least-squares refinement of 750 diffractometry data with I≥2.0σ(I) gave R1 2.4% and R2 3.0% Both of these compounds were independently synthesized and Spectroscopically characterized by Köpf and co-workers, and-a Complete X-ray diffraction study was performed by Epstein and Bernal on a different monoclinic phase of Ti(h5?C5H5)2S5 (isolated by-Köpf). An extraction of V(h5?C5H5)2S5 with re fluxing benzene under nitrogen atmosphere in a Soxhlet apparatus led to the formation of the previously reported [V2 (h5?C5H5)2S5]n compound which was characterized by physical measurements including a preliminary X-ray diffraction study.  相似文献   

14.
Some newly synthesized fluorinated nitroxides, such as t-butyl perfluoroalkyl nitroxides ButN(O) Rf (Rf=CF3, 5; C2F5, 6; n-C3F7, 7) and s-butyl perfluoroacyl nitroxides BusN(O) CORf (Rf=CF3, 9; n-C3F7, 10) have been employed as ESR probes of solvation in different common organic solvents. In aprotic solvents, the measured aN values for each of the nitroxyl probes show a linear correlation with the cybotactic polar solvent parameters ET (Dimroth) and Z (Kosowar), i.e. aN=bET+c, and aN=bZ+c′. The physical significance for the slope (b or b′), the slope×ET or slope×Z, the extrapolated intercept on aN axis, c or c′, are linked, respectively, to the sensitivity of a specific nitroxide toward solvation, the magnitude of the overall solvation effect on the aN value, and the intrinsic aN value of each nitroxide in the ideal gaseous state. The intercept on the aN axis may also serve as a new measure of electronegativity for perfluoroalkyl groups, CF3, C2F5, n-C3F7, and perfluoroacyl groups, CF3CO, n-C3F7CO. In protic solvents, i.e. alcohols and carboxylic acids, however, aN values of all the probes, kept almost no change with the increase in ET and Z. Furthermore, the plots of aN versus non-cybotactic solvent constants, such as dipolar moment (μ) and dielectric constant (ε), all show random variations.  相似文献   

15.
Uncompensated resistance (Ru) has a distoring effect on normalized potential sweep voltammetry (NPSV) slopes. This provides a simple and effective method to determine Rfo, the value of the potentiostat feedback resistance necessary for full compensation. If the NPSV range is divided into overlapping segment, 1 and 2, corresponding to IN of 0.20–0.50 and 0.50–0.80 respectively, the slopes m1 and m2 differ significantly when Rf differs form Rfo. The difference, m1-m2, is negative for Rf<Rfo and positive for Rf>Rfo. Fine tuning of the potentiostat Rf setting so that the average value of the difference is the theoretical value can be accomplished in a minimum of time. Under these conditions, m1 and m2, as well as mT, the slope of the entire correlation have very nearly the same values. Linear equations were derived from theoretical data which allow heterogeneous rate constants to be obtained directly from NPSV slopes. The precision in the NPSV slopes was observed to be of the order of ±0.002 which implies that the method should give reliable rate constants as great as 10cm s? at a voltage sweep rate of 100V s?1. The method is demonstrated using the reduction of benzonitrile and perylene in N,N-dimethylformamide and acetonitrile as examples.  相似文献   

16.
Two hydrated uranyl arsenates and a uranyl phosphate were synthesized by hydrothermal methods in the presence of amine structure-directing agents and their structures determined: (N2C6H14)[(UO2)(AsO4)]2(H2O)3, DabcoUAs, {NH(C2H5)3}[(UO2)2(AsO4)(AsO3OH)], TriethUAs, and (N2C4H12)(UO2)[(UO2)(PO4)]4(H2O)2, PiperUP. Intensity data were collected at room temperature using MoKα X-radiation and a CCD-based area detector. The crystal structures were refined by full-matrix least-squares techniques on the basis of F2 to agreement indices (DabcoUAs, TriethUAs, PiperUP) wR2=5.6%, 8.3%, 7.2% for all data, and R1=2.9%, 3.3%, 4.0%, calculated for 1777, 5822, 9119 unique observed reflections (|Fo|?4σF), respectively. DabcoUAs is monoclinic, space group C2/m, Z=2, a=18.581(1), b=7.1897(4), c=7.1909(4) Å, β=102.886(1)°, V=936.43(9) Å3, Dcalc=3.50 g/cm3. TriethUAs is monoclinic, space group P21/n, Z=4, a=9.6359(4), b=18.4678(7), c=10.0708(4) Å, β=92.282(1)°, V=1790.7(1) Å3, Dcalc=3.41 g/cm3. PiperUP is monoclinic, space group Pn, Z=2, a=9.3278(4), b=15.5529(7), c=9.6474(5) Å, β=93.266(1)°, V=1397.3(1) Å3, Dcalc=4.41 g/cm3. The structure of DabcoUAs contains the autunite-type sheet formed by the sharing of vertices between uranyl square bipyramids and arsenate tetrahedra. The triethylenediammonium cations are located in the interlayer along with two H2O groups and are disordered. Both TriethUAs and PiperUP contain sheets formed of uranyl pentagonal bipyramids and tetrahedra (arsenate and phosphate, respectively) with the uranophane sheet-anion topology. In TriethUAs, triethlyammonium cations are located in the interlayer. In PiperUP, the sheets are connected by a uranyl pentagonal bipyramid that shares corners with phosphate tetrahedra of adjacent sheets, resulting in a framework with piperazinium cations and H2O groups in the cavities of the structure.  相似文献   

17.
The low-resolution mass spectra of 13 trifluoromethyl and/or methyl sulfur-containing compounds (CF3SnCF3, CF3SnCH3, CH3SnCH3, CF3SmCl, and CH3SmCl; n = 1, 2, 3; m = 1, 2) are reported and discussed. There is a considerable similarity between the fragmentation pattern of compounds with the same terminal groups. However, with a fluorinated and a non-fluorinated methyl group, the major fragmentation products produced are similar to those for the dimethyl compounds.  相似文献   

18.
The symmetry of Kekulé structures for aromatic hydrocarbons is studied by group theory. The general problem of deducing the distribution over irreducible representations (ΛKek) or characters of the representation based on the Kekulé structures (χKek) has not been solved. A partial solution is given for two classes of molecules, namely (a) the “straight chain” aromatics (polyacenes): naphthalene, anthracene, naphthacene, etc., and (b) the “zig-zag chain” aromatics: phenanthrene, chrysene, picene, etc. As a part of this solution the number of Kekulé structures (K) in the two cases was found to be (a) K = Q + 1 and (b) K = FQ+1, respectively. Here Q is the number of benzene rings in the molecule in question, and Fi denotes the i-th member of the Fibonacci series. Symmetrical structures (ΛKek) or characters (χKek) are given for a number of additional molecules as examples: benzene (D6h), tetraphene (Cs), benzo[c] phenanthrene (C2v), pyrene (D2h), triphenylene (D3h), perylene (D2h), pentaphene (C2v), dibenzophenanthrene (C2v), heptaphene (C2v) and coronene (D6h). Here the appropriate symmetry groups are given in parentheses.  相似文献   

19.
The infrared and Raman spectra of azodicarbonitrile (I) made from cyanogen azide (II) were recorded under varied conditions of phase, temperature, concentration, and pressure and strongly indicate a C2h symmetry (trans-(I)). Cis-(I) was not shown positively either by these techniques or by microwave spectra. The fundamental vibration frequencies tentatively suggested for trans-(I) are (cm−1): v1 = 2176, v2 = 1422, v3 = 1002, v4= 741, v5 = 282 (Ag), v6 = 108 (Bg, v7 = 2204, v8 = 982, v9 = 904, v10 = 596 (Bu), v11 = 574, v12 = 133 (Au). Of these, v4 and v6 were not observed directly, but inferred from an analysis of a complex band in the infrared spectrum.  相似文献   

20.
ABOX niobates and titanates belonging to the homologous series AnBnO3n+2 are a special group of perovskite-related layered materials. These oxides comprise the highest-Tc ferroelectrics such as CaNbO3.50 and LaTiO3.50, as well as thermodynamically stable bulk compounds involving well-ordered stacking sequences of layers with different thickness such as SrNbO3.45. An extensive overview on many ABOX compositions of the AnBnO3n+2 family and its properties is presented. The crystal structure type is given by n and can be tuned by adjusting the oxygen content X. The charge carrier concentration of the electrical conducting oxides can be varied by appropriate substitutions at the A or B site. To investigate the properties of these systems, more than 150 different compositions were prepared. Most of them were grown by floating zone melting, of which many were fabricated as single crystals with precise control of the oxygen content X. For these crystalline compounds, the synthesis, structural, electric and magnetic features are discussed. Attempts to prepare series members beyond the known structure types n=4, 4.33, 4.5, 5 and 6 were not successful. For some of the known structures types n, however, pronounced non-stoichiometric homogeneity ranges with respect to the oxygen content X and cation ratio A/B were found. Thus, these systems offer many possibilities to vary the compositional, structural, chemical and physical properties. Further, measurements of the resistivity as a function of temperature T are reported for crystals of the n=4 type Sr0.8La0.2NbO3.50, n=4.5 type Sr0.96Ba0.04NbO3.45 and n=5 types Sr1−YLaYNbO3.41 (Y=0, 0.035, 0.1), Sr0.95NbO3.37, CaNbO3.41 and LaTiO3.41. These measurements, which were performed in the temperature range 4 K≤T≤290 K and along the a-, b- and c-axis, revealed a highly anisotropic conductivity and intricate behavior. In parts of the temperature range, these materials are quasi-1D metals which display temperature-driven metal-semiconductor transitions at lower temperatures. The niobates and titanates investigated represent a new group of quasi-1D metals which are in compositional, structural and electronical proximity to non-conducting layered (anti)ferroelectrics. Furthermore, measurements of the magnetic susceptibility as a function of temperature are reported for many compounds. As a typical property at elevated temperatures, it was observed that the magnetic susceptibility rises with increasing temperature.  相似文献   

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