Ionic conductivity of ScF<Subscript>3</Subscript> single crystals (ReO<Subscript>3</Subscript> type)

Electrical conductivity σ of ScF₃ single crystals (sp. gr. \(Pm\overline 3 m\), ReO₃ structure type) has been studied by impedance spectroscopy and compared with the electrical conductivity of rare earth HoF₃ (β-YF₃ type) and LaF₃ (tysonite type) trifluorides. ScF₃ crystals obtained by Bridgman directional solidification have ionic conductivity σ = 4 × 10^–8 S/cm at 673 K. It is smaller than the σ values for LaF₃ (sp. gr. \(P\overline 3 c1\)) and HoF₃ (sp. gr. Pnma) single crystals by a factor of 10⁴–10⁵. The low conductivity of ScF₃ crystals is due to the weak coordinating ability (coordination number CN = 6) and low electronic polarizability (α_cat = 1.1 ų) of Sc³⁺ ions. Mobile V_F⁺ vacancies and less mobile interstitial V_i^- ions (defects are formed according to the Frenkel mechanism) are involved in the ion transport. HoF₃ and LaF₃ single crystals have a high coordinating ability (CN = 9 for Ho³⁺ and CN = 11 for La³⁺) and a high electronic polarizability of cations (α_cat = 1.6–1.9 ų for Ho³⁺ and α_cat = 2.2 ų for La³⁺). Only mobile V_F⁺ vacancies (defects are formed according to the Schottky mechanism) are involved in ion transport.     

Resonance Paramagnetique Electronique: Etude au Moyen d'une Sonde Radicalaire Nitroxyde Deuteree,de l'Orientation Macroscopique et Microscopique des Phases Isotrope et Nematique de l'E.B.B.A.

Abstract

Les spectres de R.P.E. d'une sonde nitroxyde deutérée, de forme allongée, ont été analysés dans les phases isotrope et nématique de l'E.B.B.A.

Les résultats expérimentaux concernant la mesure des paramètres d'ordre et la réorientation moléculaire sont en bon accord avec l'utilisation d'un potentiel décrivant l'orientation moléculaire, de la forme U=u ₂ (P ₂P₂ + λP ₄P₄).

La détermination des temps caractéristiques de la réorientation moléculaire τ₂₀ et τ₂₂ montre qu'ils ne subissent pas de variations notables lorsque I'on passe de la phase isotrope é la phase nématique. L'ordre local à l'échelle microscopique du cristal liquide ne subit donc pas de profondes modifications de part et d'autre de la transition. D'autre part, sauf au voisingage du point de clarification les temps de corrélation pour la réorientation du grand axe moléculaire de la sonde obéissant à la loi usuelle: τ₂₀=(τ₂₀) _oe -^?E/kT avec E=8.5 kcal/mole dans la phase isotrope et E=9 kcal/mole dans la phase nématique.

The E.S.R. spectra of a long shaped deuterated nitroxide probe dissolved in the isotropic and the nematic phases of E.B.B.A. have been studied.

Experimental and theoretical results for anisotropic ordering and molecular motions are able to achieve good fits by means of an orientational potential like this described by Humphries et al.: U=z ₂(P ₂ + λP ₄,P₄).

The determination of the rotational correlation times τ₂₀ and τ₂₂ of the probe shows that no important discontinuity occurs for the local ordering structure of the liquid crystal when one goes through the isotropic-nematic transition. Relatively far of this transition the correlation time τ₂₀ obeys the classic temperature dependence: τ₂₀=(τ₂₀)oe ^?E/kT with E=8.5 k cal/mole in the isotropic phase and E=9 kcal/mole in the nematic phase.     

On the effect of structural and symmetrical features of potassium titanyl phosphate crystals with different contents of niobium,antimony, and zirconium on the second-harmonic intensity

A model is proposed, which shows that, at small deviations from the centrosymmetric state of the atomic structure, the quadratic nonlinear susceptibility of a crystal monotonically decreases with approach of the degree of central symmetry \(\eta _{\overline 1 } \)[φ(r)] of the electric potential function of the crystal structure to unity. The quadratic nonlinear susceptibility of K_{1 ? x} Ti_{1 ? x} Nb _x OPO₄ (x = 0, 0.02, 0.04, 0.11), K_{1 ? x} Ti_{1 ? x} Sb _x OPO₄ (x = 0.01, 0.07, 0.17), and KTi_{1 ? x} Zr _x OPO₄ (x = 0.03, 0.04) crystals has been measured. The degree of central symmetry \(\eta _{\overline 1 } \)[φ(r)] has been calculated for the structures of K_{1 ? x} Ti_{1 ? x} Nb _x OPO₄ (x = 0, 0.04, 0.11), K_{1 ? x} Ti_{1 ? x} Sb _x OPO₄ (x = 0.01, 0.07, 0.17), and KTi_{1 ? x} Zr _x OPO₄ (x = 0.03, 0.04) crystals. It is shown that, at \(\eta _{\overline 1 } \)[φ(r)] > 0.7, the relationship between the quadratic nonlinear susceptibility of the investigated crystals and the degree of their central symmetry \(\eta _{\overline 1 } \)[φ(r)] is in qualitative agreement with the proposed model.     

Manifestation of optical activity at oblique incidence of light in crystals of classes $$\overline 4 $$2 m and $$\overline 4 $$

The polarization azimuths and ellipticities of the reflected and transmitted light have been calculated as functions of the angle of incidence for transparent crystals of classes \(\overline 4 \)2m and \(\overline 4 \). Analytical expressions for these parameters are obtained. It is shown that in the general case the polarization azimuths and ellipticities for a plate cut parallel to the optical axis differ for positive and negative angles of incidence of light.     

Synthesis, growth and characterization of nonlinear optical crystal: l-tyrosine hydrobromide

l-tyrosine hydrobromide (l-THB) a semi organic nonlinear optical material with molecular formula C₉H₁₂NO₃Br has been synthesized at ambient temperature. Spectral, thermal and optical techniques have been employed to characterize the new material. The solubility of l-THB at varying temperatures was determined in different concentrations of hydrobromic acid. Bulk single crystals of size 15×7×4 mm³ of l-THB were grown by slow evaporation method at constant temperature. Powder X-ray diffraction pattern of the grown l-THB has been indexed. Functional groups present in the sample were identified by FTIR spectral analysis. Chemical composition of the synthesized material was confirmed by carrying out CHN analysis. Thermal stability of l-THB was determined from TGA/DTA and DSC response curves. Mechanical hardness of the grown crystal l-THB was determined and Vickers hardness number was calculated. The Kurtz powder second harmonic generation test shows that the compound is a potential candidate for optical second harmonic generation. The optical transparency range and the lower cut-off of UV transmission were identified from the recorded UV-vis spectrum of l-THB. The optical energy gap of l-THB is 3 eV.     

Crystal structure of Сu<Subscript>4</Subscript>SeTe

Сu₄SeTe compound has been synthesized. A Сu₄SeTe sample was homogenized by annealing at 750 K for five days. An X-ray diffraction analysis based on powder diffraction data has revealed that the sample crystallizes into the trigonal system with lattice parameters а = 4.178 Å and с = 41.921 Å, sp. gr. \(R\overline 3 m\), Z = 6. Its crystal structure has been determined and refined by the Rietveld method. The final value of the reliability factor R _Bragg is found to be 0.0246.     

Synthesis and X-ray diffraction study of new uranyl malonate and oxalate complexes with carbamide

Two new malonate-containing uranyl complexes with carbamide of the formulas [UO₂(C₃H₂O₄)(Urea)₂] (I) and [UO₂(C₃H₂O₄)(Urea)₃] (II), where Urea is carbamide, and one uranyl oxalate complex of the formula [UO₂(C₂O₄)(Urea)₃] (III) were synthesized, and their crystals were studied by X-ray diffraction. The main structural units in crystals I are the electroneutral chains [UO₂(C₃H₂O₄)(Urea)₂]_∞ belonging to the crystal-chemical group AT¹¹M₂¹ (A = UO₂²⁺, T¹¹ = C₃H₂O₄^2-, M¹ = Urea) of uranyl complexes. Crystals II and III are composed of the molecular complexes [UO₂(L)(Urea)₃], where L = C₃H₂O₄^2- or C₂O₄^2-, belonging to the crystal-chemical group AB⁰¹M₃¹ (A = UO₂²⁺, B⁰¹ = C₃H₂O₄^2- or C₂O₄^2-, M¹ = Urea). The characteristic features of the packing of the uranium-containing complexes are discussed in terms of molecular Voronoi–Dirichlet polyhedra. The effect of the Urea: U ratio on the structure of uranium-containing structural units is considered.     

Synthesis and crystal structure of Na<Subscript>3</Subscript>(H<Subscript>3</Subscript>O)[UO<Subscript>2</Subscript>(SeO<Subscript>3</Subscript>)<Subscript>2</Subscript>]<Subscript>2</Subscript>· H<Subscript>2</Subscript>O

Single crystals of the compound Na₃(H₃O)[UO₂(SeO₃)₂]₂ · H₂O (I) have been synthesized, and their structure has been investigated using X-ray diffraction. Compound I crystallizes in the triclinic system with the unit cell parameters a = 9.543(6)Å, b = 9.602(7)Å, c = 11.742(8)Å, α = 66.693(16)°, β = 84.10(2)°, γ = 63.686(14)°, space group P \(\bar 1\), Z = 2, and R = 0.0734. The uranium-containing structural units of the crystals are [UO₂(SeO₃)₂]^2? chains, which belong to the crystal-chemical group AB ² B ¹¹ (A = UO ₂ ²⁺ , B ² = SeO ₃ ^2? , B ¹¹ = SeO ₃ ^2? ) of the uranyl complexes. The structures of the compounds containing the [UO₂(SeO₃)₂]^2? anionic complexes are compared.     

Specific features of the crystal structure and magnetic properties of KTaO<Subscript>3</Subscript> produced by electrolysis of melts

The magnetic susceptibility χ(T) at 4.2 K < T < 293 K; the dependence of the magnetic moment on the magnetic field strength, M(H), at 4.2, 77, and 293 K; and the electrical resistivity ρ(T) at 4.2 K < T < 293 K are studied for samples of perovskite-phase KTaO₃ obtained by both solid-phase synthesis (KTaO ₃ ^s ) and deposition on a cathode during electrolysis of melts (KTaO ₃ ^e ). Yellowish white KTaO ₃ ^s powders are diamagnetic and reveal dielectric properties. Dark polycrystalline KTaO ₃ ^e samples with metallic luster are characterized by the dependence ρ(T) typical of metals and additional paramagnetic contribution to the paramagnetic susceptibility as compared with KTaO ₃ ^e . Changes in the properties of KTaO₃ during electrocrystallization are attributed to partial reduction of tantalum. They are revealed in the structural features of KTaO ₃ ^e (excess of tantalum as compared to the stoichiometric composition of KTaO ₃ ^e , deficiency of the oxygen sublattice, and clearly pronounced anharmonicity of atomic vibrations). A change of the cation-anion-cation interactions, occurring owing to the overlapping of oxygen p orbitals with tantalum t_2g orbitals and the formation of impurity levels near the conduction band, leads to the generation of free carriers, which make a paramagnetic contribution to the magnetic susceptibility.     

Refinement of the crystal structures of synthetic nickel- and cobalt-bearing tourmalines

The crystal structures of synthetic tourmalines with a unique composition containing 3d elements (Ni, Fe, and Co) have been refined: (Ca_0.12?_0.88)(Al_1.69Ni _0.81 ²⁺ Fe _0.50 ²⁺ )(Al_5.40Fe _0.60 ³⁺ )(Si_5.82Al_0.18O₁₈)(BO₃)₃(OH)_3.25O_0.75 I, a = 15.897(5), c = 7.145(2) Å, V = 1564(1) Å; Na_0.91(Ni _1.20 ²⁺ Cr _0.96 ³⁺ Al_0.63Fe _0.18 ²⁺ Mg_0.03)(Al_4.26Ni _1.20 ²⁺ Cr _0.48 ³⁺ Ti_0.06)(Si_5.82Al_0.18)O₁₈(BO₃)₃(OH)_3.73O_0.27 II, a = 15.945(5), c = 7.208(2) Å, V = 1587(1) ų and Na_0.35(Al_1.80Co _1.20 ²⁺ )(Al_5.28Co _0.66 ²⁺ Ti_0.06)(Si_5.64B_0.36)O₁₈(BO₃)₃(OH)_3.81O_0.19 III, a = 15.753(8), c = 7.053(3) Å, V = 1516(2) ų. The reliability factors are R ₁ = 0.038?0.057 and wR ₂ = 0.041–0.060. It is found that 3d elements occupy both Y- and Z positions in all structures. The excess positive charge is compensated for due to the incorporation of divalent oxygen anions into the O3(V)+O1(W) positions.     

Distortions of the atomic structure of 2/1 approximants of icosahedral quasicrystals

Ideal structures of several 2/1 approximants of icosahedral quasicrystals with the sp. gr. Pm \(\overline 3 \) and Pa \(\overline 3 \) have been constructed. It is shown that most atoms have dodecadhedral local coordination. The structural features of the crystals studied have been analyzed. It is found that displacements of atoms from ideal positions in real crystals tend to increase with an increase in the distance to the center of the approximant projection on the perpendicular space. Large displacements are generally related to the presence of very close neighbors in the ideal structure of the approximant. The importance of the investigation of approximants as a source of information about the structure of polyatomic nanoclusters is indicated.     

The effect of tourmaline additives in TiO2 photoanode for high-efficiency dye sensitized solar cells

Tourmaline is a kind of borosilicatemineral and has spontaneous polarization property. Due to this property, it can generate a feeble current around 0.06 mA[1 O'Regan, B., &; Grätzel, M. (1991). Nature 353, 737.[Crossref], [Web of Science ®] , [Google Scholar]]. We fabricated the TiO₂ photoanode with different wt.% ratio of tourmaline and investigated the effect of tourmaline additive on dye sensitized solar cells (DSSCs). We carried out electrochemical impedance spectroscopy (EIS) and current density-voltage (J-V) measurement. The results showed that the electron lifetime and the power conversion efficiency of the DSSCs with TiO₂ photoanode containing 3wt% tourmaline were enhanced by about 42% and 20%, respectively, as compared to the DSSCs using pristine TiO₂ photoanode.     

Viscous and elastic properties of the nematic in the tetrapalladium organyl-pentadecane system

Temperature dependences of the dielectric anisotropy ?_a, effective rotational viscosity \(\tilde \gamma \), and elastic modulus K ₁₁ of the nematic phase of the tetrapalladium organyl-pentadecane system containing 55 wt % pentadecane have been experimentally studied. The quantities ?_a, \(\tilde \gamma \), and K ₁₁ are shown to decrease: ?_a decreases by a factor of about 2.5; \(\tilde \gamma \), by almost two orders of magnitude; and K ₁₁, by more than an order of magnitude. It is found that an applied electric field induces growth of tetrapalladium organyl crystals at 6–9°C above the nematic-crystallosolvate phase transition temperature.     

The crystal structure of racemicdl-penicillamine and a spectroscopic study ofd-(−)-penicillamine

The X-ray crystal structure of a racemic mixture of D- and L-penicillamine has been determined. Crystals are monoclinic,P2₁/c (No. 14), with cell dimensionsa=11.624(3),b=5.919(1),c=11.482(2) Å,β=114.48(2)°, andZ=2, based on the racemate. The structure was determined by standard methods and refined toR ₁=0.0666,R ₂=0.0726 for 985 independent reflections. Bond lengths and bond angles do not differ from those in similar structures. Mass spectra and¹H and¹³C NMR spectra are reported ford-penicillamine, and detailed infrared and Raman spectra are reported for solidd-penicillamine hydrochloride,d ₅-d-penicillamine hydrochloride,d-penicillamine,d ₄-d-penicillamine, anddl-penicillamine. The Raman spectrum ofd-penicillamine in H₂O solution as a function of pH is also reported.     

Reaction of 2,3-bis(diphenylphosphino)maleic acid-thioanhydride (bmata) with PhCCo3(CO)9. X-ray diffraction structure of {\text{Co}}_{\text{3}} ({\text{CO)}}_{\text{6}} [\mu _2 ,\eta ^2 ,\eta ^1 {\text{ - C(Ph)}}{\text{(O)](}}\mu _2 {\text{ - PPh}}_{\text{2}} )

The benzylidyne-capped cluster PhCCo₃(CO)₉ (1) reacts with the diphosphine ligand 2,3-bis(diphenylphosphino)maleic acid-thioanhydride (bmata) to afford ultimately the new cluster ${\text{Co}}_{\text{3}} ({\text{CO)}}_{\text{6}} [\mu _2 ,\eta ^2 ,\eta ^1 {\text{ - C(Ph)}}{\text{(O)](}}\mu _2 {\text{ - PPh}}_{\text{2}} )$ (3) in low yield under thermolysis conditions or by Me₃NO activation of PhCCo₃(CO)₉. The intermediate cluster compound PhCCo₃(CO)₇(bmata) (2) has been confirmed by IR spectroscopy and is shown to give ${\text{Co}}_{\text{3}} ({\text{CO)}}_{\text{6}} [\mu _2 ,\eta ^2 ,\eta ^1 {\text{ - C(Ph)}}{\text{(O)](}}\mu _2 {\text{ - PPh}}_{\text{2}} )$ upon heating. Cluster 3 has been isolated and characterized in solution by IR and ³¹P NMR spectroscopies, and the solid-state structure of 3 was established by X-ray diffraction analysis. ${\text{Co}}_{\text{3}} ({\text{CO)}}_{\text{6}} [\mu _2 ,\eta ^2 ,\eta ^1 {\text{ - C(Ph)}}{\text{(O)](}}\mu _2 {\text{ - PPh}}_{\text{2}} )$ crystallizes in the triclinic space group P ${\bar 1}$ , a = 11.6053(8) Å, b = 11.8438(8) Å, c = 15.099(1) Å, α = 105.169(5)^○, β = 90.530(5)^○, γ = 104.976(6)^○, V = 1928.5(2) ų, Z = 2, and d _calc = 1.578; R = 0.0442, R _w = 0.481 for 2591 observed reflections with I > 3σ (I). The cyclic voltammetric properties of 3 have been investigated and are contrasted with the related bma-derived cluster ${\text{Co}}_{\text{3}} ({\text{CO)}}_{\text{6}} [\mu _2 ,\eta ^2 ,\eta ^1 {\text{ - }}{\text{(O)OC(O)](}}\mu _2 {\text{ - PPh}}_{\text{2}} )$ .     

Separate determination of the amplitude of thermal vibrations and static atomic displacements in titanium carbide by neutron diffraction

The amplitude of thermal (dynamic) atomic vibrations and meansquare static atomic displacements in titanium carbide TiC _x (x = 0.97, 0.88, 0.70) have been separately determined by measuring neutron diffraction patterns at two temperatures (T ₁ = 300 K and T ₂ = 80 K). The static lattice distortions in stoichiometric titanium carbide are experimentally found to be negligible. In the TiC _x homogeneity range, the amplitude \(\sqrt {\overline {u_{dyn}^2 } } \) of thermal atomic vibrations significantly increases with a decrease in the carbon concentration. The Debye temperature has been determined for the first time in the TiC _x homogeneity range at both room and liquid-nitrogen temperatures.     

Study of the nanosiderite from ferruginous quartzites of Kursk magnetic anomaly by transmission electron microscopy

Biogenic siderite consisting of equally crystallographically oriented disklike nanoparticles 5–20 nm in size has been found (using transmission electron microscopy) in oxidized ferruginous quartzites (jaspilites) of the Lebedinsky field of the Kursk magnetic anomaly. Based on microdiffraction data and highresolution images, lowering of the siderite structure symmetry from \(R\overline 3 c\) to \(R\overline 3 \) has been established for the first time. A siderite structure model is proposed to explain this fact. Within this model, vacancies formed as a result of oxidation of some part of Fe²⁺ cations to the Fe³⁺ state are ordered in one of two nonequivalent octahedral sites. Identical crystallographic orientation and nanoparticle morphology have been established for coexisting siderite and hematite. It is suggested that the revealed specific features of nanosiderite are related to its biogenic origin.     

Crystal structure of new synthetic Ca,Na,Li-carbonate-borate

In the process of studying the phase formation in the Li₂CO₃-CaO-B₂O₃-NaCl system, new Ca,Na, Li-carbonate-borate has been synthesized under hydrothermal conditions. The crystal structure of carbonate-borate with the crystallochemical formula Ca₄(Ca_0.7Na_0.3)₃(Na_0.7□ _0.3)Li₅[B ₁₂ ^t B ₁₀ ^Δ O₃₆(O,OH)₆](CO₃)(OH) · (OH,H₂O) was refined to R _hkl = 0.0716 by the least squares method in the isotropic approximation of atomic thermal vibrations without the preliminary knowledge of the chemical composition and the formula (sp. gr. R3, a _rh = 13.05(2) Å, α = 40.32(7)]°, V = 838(2) ų, a _h = 8.99(2), c _h = 35.91(2) Å, V = 2513(2) ų, Z = 3, d _calcd = 2.62 g/cm³, Syntex P $\bar 1$ diffractometer, 3459 reflections, 2θ-θ method, λMo). The structure has a new boron-oxygen radical [B ₁₂ ^t B ₁₀ ^Δ O₃₆(O,OH)₆] _∞∞ ^15? , a double layer of nine-membered [B ₆ ^t B ₃ ^Δ O₁₅(O,OH)₃]^7.5?-rings bound by BO₃-triangles, and twelve-membered [B ₆ ^t B ₆ ^Δ O_19.5(O,OH)₃]^7.5? rings. This allows one to relate this compound to megaborates with complex boron-oxygen radicals. The structure is built from two types of blocks consisting of Ca,Na,B-and Li,B-polyhedra alternating along the c-axis, which explains the perfect cleavage of the crystals along the (0001) plane.     

A Two-Dimensional Coordination Polymer Based on 1,1':4',1'-Terphenyl-2',4,4',5'-tetracarboxylate

The coordination polymer, [MnL_0.5(H₂O)(phen)] _n (H₄L = 1,1':4',1''-terphenyl-2',4,4'',5'-tetracarboxylic acid, phen = 1,10-phenanthroline), has been solvothermal synthesized and structurally characterized by single-crystal X-ray diffraction. Complex crystallizes in triclinic sp. gr.\(P\bar 1\) with Z = 2. Two carboxylate oxygen atoms in the central phenyl rings from two μ\({u_{{6^ - }}}\)L^4– ligands doubly-bridge two Mn(II) ions to form the dinuclear \(M{n_2}{({O_{CO{O^ - }}})_2}\) unit. Each dinuclear \(M{n_2}{({O_{CO{O^ - }}})_2}\) unit links four L^4– ligands and each L^4–ligand bridges four dinuclear \(M{n_2}{({O_{CO{O^ - }}})_2}\) units to generate a 2D coordination network, which can be rationalized as a binodal (4,4) topological network by considering the dinuclear \(M{n_2}{({O_{CO{O^ - }}})_2}\) units and L^4– ligands as 4-connected nodes.