Role of electronic effects in forming the structure of the nitrilotrismethylenephosphonic complexes of 3<Emphasis Type="Italic">d</Emphasis> elements (Cr–Zn)

Two series of nitrilotrismethylenephosphonic complexes of 3d elements, [MII(H₂O)₃{NH(CH₂PO₃H)₃}]_n (M = Cr–Zn) and Na₈[MII{N(CH₂PO₃)₃}]₂ nH₂O (M = Co–Zn), are studied. A comparative analysis of their structural features showed the influence the Jahn–Teller effect has on the formation of the crystal structures, reactive capacities, and anticorrosive activities of these compounds.     

Effect of cation substitution in Cs<Subscript>1–2<Emphasis Type="Italic">x</Emphasis></Subscript>Ba<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>H<Subscript>2</Subscript>PO<Subscript>4</Subscript> on structural properties and proton conductivity

We synthesized compounds with partial substitution of Cs⁺ cations in CsH₂PO₄ by Ba²⁺ cations. The structural, electron transport and thermodynamic properties of Cs_1–2x Ba _x H₂PO₄ (x = 0–0.15) were studied for the first time with the help of a set of physicochemical methods: infrared and impedance spectroscopy, X-ray diffraction and synchronous thermal analysis. The proton conductivity of Cs_1–2x Ba _x H₂PO₄ at 50–230°C was investigated in detail by impedance measurements. The formation of solid substitution solutions isostructural with CsH₂PO₄ (P2₁/m) is observed in the range of substitution degrees of x = 0–0.1, with a slight decrease in the unit cell parameters and some salt amorphization. The conductivity of disordered Cs_1–2x Ba _x H₂PO₄ in the low-temperature region increases by two orders of magnitude at x = 0.02 and increases with an increasing fraction of barium cations by three or four orders of magnitude at x = 0.05–0.1; the superionic phase transition practically disappears. At x = 0.15, heterophase systems based on salts are formed, showing high conductivity and a further decrease in the activation energy of conductivity to 0.63 eV. The conductivity of the high-temperature phase of Cs_1–2x Ba _x H₂PO₄ does not change with increasing fraction of the substituent.     

Proton conductivity and phase composition of mixed salts in the systems <Emphasis Type="Italic">M</Emphasis>H<Subscript>2</Subscript>PO<Subscript>4</Subscript>–CsHSO<Subscript>4</Subscript> (<Emphasis Type="Italic">M</Emphasis> = Cs,K)

Phase transformations, electrical transport and thermal properties of the systems K_1?xCs_x(H₂PO₄)_1–x(HSO₄)_x (x = 0.01–0.95) and Cs(H₂PO₄)_1–x(HSO₄)_x (x = 0.01–0.30) have been studied in detail. It has been shown that the mixed compounds Cs(H₂PO₄)_1–x(HSO₄)_x are characterized by an increase in the low-temperature electrical conductivity by one to five orders of magnitude depending on the composition, as well as by the disappearance of the superionic phase transition at x ≥ 0.15. The partial substitution of HSO₄^- ions for the anions in CsH₂PO₄ at x = 0.01–0.10 leads to the formation of Cs(H₂PO₄)_1?x(HSO₄)_x solid solutions isostructural with the CsH₂PO₄ (P2₁/m) phase. For Cs(H₂PO₄)_1–x(HSO₄)_x with x = 0.15–0.30 at room temperature, there is a stabilization of the high-temperature cubic phase isostructural with the CsH₂PO₄ (\(Pm\overline 3 m\)) phase existing in CsH₂PO₄ at temperatures above 230°C. The stability of the \(Pm\overline 3 m\) cubic phase at room temperature has been investigated using X-ray powder diffraction, ¹H NMR spectroscopy, and impedance spectroscopy. In the K_1–xCs_x(H₂PO₄)_1–x(HSO₄) system, there are two regions of compositions with x = 0.05–0.50 and 0.60–0.95, where the proton conductivity and thermal properties are determined respectively by the formation of the CsH₅(PO₄)₂ phase, which is stoichiometrically different from the initial salts, and the potassium-containing phase, which is isostructural with the superionic salt Cs₃(HSO₄)₂(H₂PO₄).     

Polarized IR and Raman spectra of (H<Subscript>2</Subscript>O)<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> clusters (<Emphasis Type="Italic">n</Emphasis> = 2–5) in the <Emphasis Type="Italic">c</Emphasis>-channels of apatite single crystals

The infrared (IR) and Raman spectra of three samples of fluorapatite single crystals and carbonate fluorapatite single crystal in the region of 7000–400 cm^–1 were studied. It has been shown that isomorphic substitution of the Ca²⁺ cation and the PO₄^3- anion leads to an increase in the size of the c-channels in the apatite crystal, which is accompanied by the formation of water clusters of the (H₂O) _n and H₃O⁺ · (H₂O) _n (n = 2–5) types as a result of the diffusion processes in these local sections of the c-channels.     

Magnetostriction of Hexagonal HoMnO<Subscript>3</Subscript> and YMnO<Subscript>3</Subscript> Single Crystals

We report on the magnetostriction of hexagonal HoMnO₃ and YMnO₃ single crystals in a wide range of applied magnetic fields (up to H = 14 T) at all possible combinations of the mutual orientations of magnetic field H and magnetostriction ΔL/L. The measured ΔL/L(H, T) data agree well with the magnetic phase diagram of the HoMnO₃ single crystal reported previously by other authors. It is shown that the nonmonotonic behavior of magnetostriction of the HoMnO₃ crystal is caused by the Ho³⁺ ion; the magnetic moment of the Mn³⁺ ion parallel to the hexagonal crystal axis. The anomalies established from the magnetostriction measurements of HoMnO₃ are consistent with the phase diagram of these compounds. For the isostructural YMnO₃ single crystal with a nonmagnetic rare-earth ion, the ΔL/L(H, T) dependences are described well by a conventional quadratic law in a wide temperature range (4–100 K). In addition, the magnetostriction effect is qualitatively estimated with regard to the effect of the crystal electric field on the holmium ion.     

Electronic energy structure and x-ray spectra of wide-gap AlN and BN crystals and B<Subscript>x</Subscript>Al<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>N solid solutions

The electronic energy structure of 2H and 3C AlN and BN crystals and B_xAl_1?xN solid solutions is calculated on the basis of the local coherent potential method using the cluster version of the MT approximation and the theory of multiple scattering. The features of the electronic structure of 2H-AlN crystals are compared with x-ray K and L absorption and emission spectra of aluminum and nitrogen. An interpretation of these features is given. The concentration dependences of the width of the upper subband of the valence band and the band gap in B_xAl_1?xN solid solutions (x = 0.25, 0.5, 0.75) are investigated. Charge transfer from aluminum to nitrogen atoms is shown to occur and increase with boron doping in both crystallographic modifications.     

Spectroscopy of optical centers of Eu<Superscript>3+</Superscript> ions in partially stabilized and stabilized zirconium crystals

The structure of the optical centers of Eu³⁺ ions in tetragonal (ZrO₂)_1–x–y (Y₂O₃) _x (Eu₂O₃) _y (х = 2.7–3.6; y = 0.1) and cubic (ZrO₂)_1–x–y (Y₂O₃) _x (Eu₂O₃) _y (х = 8–38; y = 0.1–0.5) crystals of solid solutions on the basis of zirconium dioxide is studied using the methods of optical and Raman-scattering spectroscopy. Characteristic optical centers of Eu³⁺ ions with different crystalline environments are revealed in the above compounds.     

Determination of the region of existence of ferromagnetic nanostructures in the paraphase of La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ba<Subscript>x</Subscript>MnO<Subscript>3</Subscript> by the EPR method

In the paraphase of a number of La_1?x Ba_xMnO₃ single crystals with 0.1 ≤ x ≤ 0.2 below 340 K, signals of the ferromagnetic resonance are observed, which indicates the presence of magnetically ordered nanoscopic objects (ferrons). The region of the existence of ferrons on the Ba density-temperature phase diagram has an approximate triangular shape, which is characteristic of the Griffiths phase. Investigations of the angular and frequency dependences of the position of the ferromagnetic resonance line indicate that the nanostructures have a spherical shape. The parameters of their magnetic anisotropy are found to be H _a1 = 2500 Oe and H _a2 = ?700 Oe.     

The effects of external influences on the distribution of polarization in calcium barium niobate crystals of differing composition

The pyroelectric properties and state of polarization of calcium barium niobate single crystals Ca_xBa_1–xNb₂O₆ (CBN) with x = 0.28, 0.30, and 0.32 are studied. It is shown that in contrast to CBN30 and CBN32 crystals, the effect of the alternating electric fields higher than the coercive field changes the state of polarization in the surface layer of the CBN28 crystal. At the same time, thermal cycling to temperatures higher than the Curie point leads to the formation of a system of antiparallel domains in CBN30 and CBN32 crystals, and to complete depolarization of CBN28 crystals.     

Constructal Design Applied to the Geometric Evaluation of an Oscillating Water Column Wave Energy Converter Considering Different Real Scale Wave Periods

The present work presents numerical study of the influence of geometry on the performance of an oscillating water column (OWC) wave energy converter by means of a constructal design. The main purpose is to maximize the root mean square hydrodynamic power of device, (P_hyd)_RMS, subject to several real scale waves with different periods. The problem has two constraints: hydropneumatic chamber volume (V _HC ) and total OWC volume (V _T ), and two degrees of freedom: H₁/L (ratio of height to length of the hydropneumatic chamber) and H₃ (OWC submergence). For the numerical solution it was used a computational fluid dynamic (CFD) code, based on the finite volume method (FVM). The multiphasic volume of fluid (VOF) model is applied to tackle with the water–air interaction. The results led to important theoretical recommendations about the design of OWC device. For instance, the best shape for OWC chamber, which maximizes the (P_hyd)_RMS, was achieved when the ratio (H₁/L) was four times higher than the ratio of height to length of incident wave (H/λ), (H₁/L) _o = 4(H/λ). Moreover, the optimal submergence (H₃) was achieved as a function of wave height (H) and water depth (h), more precisely given by the following relation: h ? (3H/4) ≤ (H₃) _o ≤ h.     

Characteristics of the Li<Superscript>+</Superscript>-Ion Conductivity of Li<Subscript>3</Subscript>R<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> Crystals (R = Fe,Sc) in the Superionic State

The characteristics of Li+-ion conductivity σdc of structural γ modifications of Li₃R₂(PO₄)₃ compounds (R = Fe, Sc) existing in the superionic state have been investigated by impedance spectroscopy. The type of structural framework [R₂P₃O₁₂]_∞^3- affects the σdc value and the σdc activation enthalpy in these compounds. The ion transport activation enthalpy in γ-Li₃R₂(PO₄)₃ (ΔH_σ = 0.31 ± 0.03 eV) is lower than in γ-Li₃Fe₂(PO₄)₃ (ΔH_σ = 0.36 ± 0.03 eV). The conductivity of γ-Li₃Fe₂(PO₄)₃ (σ_dc = 0.02 S/cm at 573 K) is twice as high as that of γ-Li₃R₂(PO₄)₃. A decrease in temperature causes a structural transformation of Li₃R₂(PO₄)₃ from the superionic γ modification (space group Pcan) through the intermediate metastable β modification (space group P2₁/n) into the “dielectric” α modification (space group P2₁/n). Upon cooling, σdc for both phosphates decreases by a factor of about 100 at the superionic TSIC transition. In Li₃Fe₂(PO₄)₃ σdc gradually decreases in the temperature range T_SIC = 430–540 K, whereas in Li₃R₂(PO₄)₃ σdc undergoes a jump at T_SIC = 540 ± 25 K. Possible crystallochemical factors responsible for the difference in the σdc and ΔH_σ values and the thermodynamics and kinetics of the superionic transition for Li₃R₂(PO₄)₃ are discussed.     

The effect of impurity on temperature variations in the refractive indices and thickness of TGS crystals

Temperature dependences of optical path difference δΔ_? and the relative changes in thickness δl_?/l of TGS crystals doped with L-valine are studied. Temperature dependences of the relative changes in refractive indices δn_?/(n–1) are calculated. The anisotropy coefficients of refractive indices А_n–1(Т) and linear expansion Аα(Т) are calculated, and a characteristic minimum of these dependences is found near the phase transition temperature.     

Heat capacity of the Pb<Subscript>5</Subscript>(Ge<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Si<Subscript>x</Subscript>)<Subscript>3</Subscript>O<Subscript>11</Subscript> ferroelectric system

The temperature dependences of the molar heat capacity at constant pressure, C_p, of Pb₅(Ge_1?xSi_x)₃O₁₁ crystals with x=0, 0.39, and 0.45 in the range 5–300 K, as well as of their permittivity, dielectric losses, and the pyroelectric effect, have been measured. Experimental data on the temperature behavior of the heat capacity are presented in the form of a sum of two Debye and one Einstein terms, C_p(T)=0.405C_D1(Θ_D1=160 K, T)+0.53C_D2(Θ_D2=750 K, T)+0.046C_E(Θ_E=47 K, T). Besides a peak in the region of the ferroelectric Curie point T_c=450 K for crystals with x=0, the temperature dependences of the heat capacity did not reveal any other pronounced anomalies.     

Effect of the Lattice and Spin-Phonon Contributions on the Temperature Behavior of the Ground State Splitting of Gd<Superscript>3+</Superscript> in SrMoO<Subscript>4</Subscript>

The temperature behavior of the EPR spectra of the Gd³⁺ impurity center in single crystals of SrMoO₄ in the temperature range T = 99–375 K is studied. The analysis of the temperature dependences of the spin Hamiltonian b ₂ ⁰ (T) = b₂(F) + b₂(L) and P ₂ ⁰ (T) = P₂(F) + P₂(L) (for Gd¹⁵⁷) describing the EPR spectrum and contributing to the Gd³⁺ ground state splitting ΔE is carried out. In terms of the Newman model, the values of b₂(L) and P₂(L) depending on the thermal expansion of the static lattice are estimated; the b₂(F) and P₂(F) spin-phonon contributions determined by the lattice ion oscillations are separated. The analysis of b ₂ ⁰ (T) and P ₂ ⁰ (T) is evidence of the positive contribution of the spin-phonon interaction; the model of the local oscillations of the impurity cluster with close frequencies ω describes well the temperature behavior of b₂(F) and P₂(F).     

Effect of gallium alloying on the structure,the phase composition,and the thermoelastic martensitic transformations in ternary Ni–Mn–Ga alloys

The effect of gallium alloying on the structure, the phase composition, and the properties of quasibinary Ni₅₀Mn_50–zGa_z (0 ? z ? 25 at %) alloys is studied over a wide temperature range. The influence of the alloy composition on the type of crystal structure in high-temperature austenite and martensite and the critical martensitic transformation temperatures is analyzed. A general phase diagram of the magnetic and structural transformations in the alloys is plotted. The temperature–concentration boundaries of the B2 and L2₁ superstructures in the austenite field, the tetragonal L1₀ (2M) martensite, and the 10M and 14M martensite phases with complex multilayer crystal lattices are found. The predominant morphology of martensite is shown to be determined by the hierarchy of the packets of thin coherent lamellae of nano- and submicrocrystalline crystals with planar habit plane boundaries close to {011}_B2. Martensite crystals are twinned along one of the 24 \(24\left\{ {011} \right\}{\left\langle {01\bar 1} \right\rangle _{B2}}\) “soft” twinning shear systems, which provides coherent accommodation of the martensitic transformation–induced elastic stresses.     

Synthesis,structural, and spectroscopic (FT-IR,NMR, and UV) Characterization of 1-(Cyclohexylmethyl)-2-(pyridin-2-yl)-1<Emphasis Type="Italic">H</Emphasis>-benzo[<Emphasis Type="Italic">d</Emphasis>]imidazole by experimental techniques and quantum chemical calculations

The title compound (II), 1-(cyclohexylmethyl)-2-(pyridin-2-yl)-1H-benzo[d]imidazole (C₁₉H₂₁N₃), was synthesized via N-alkylation of 2-(pyridin-2-yl)-1H-benzo[d]imidazole (I). Both compounds I and II were characterized by IR, NMR and UV-vis spectroscopy. Solid-state structure of compound II was determined by single-crystal X-ray diffraction technique. Furthermore, quantum chemical calculations employing density functional theory (DFT/B3LYP) method with the 6–311++G(d, p) basis set were performed for the theoretical characterization of the molecular and spectroscopic features of the compounds. Using the TD-DFT method, electronic absorption spectra of the compounds have been predicted at same level. When the obtained results were compared with the experimental findings, it is seen that theoretical results support the experimental data and a good agreement exists between them.     

The possibility of the “giant” isotope effect for ultrasound absorption in crystals

The Zeeman effect, magnetization M(H), and differential magnetic susceptibility dM/dH of ErVO₄ crystals in a pulsed magnetic field have been experimentally and theoretically studied. In magnetic fields H ∥ [001] and H ∥ [100], the energy levels of Er³⁺ ions exhibit mutual approach and crossing (the crossover effect), which results in the peaks in dM/dH and the jumps in M(H) curves at low temperatures. The anomalies in the magnetic properties related to the crossover in ErVO₄ for H ∥ [001] are highly sensitive to the electronic structure of Er³⁺ ion, which allows this effect to be used for refining the crystal field parameters. The influence of the temperature, field misorientation from the symmetry axis, parameters of pair interactions, and other factors on the magnitude and character of magnetic anomalies in ErVO₄ crystals is considered.     

Systematic Study of Vortex Pinning and a Liquid–Glass Phase Transition in BaFe<Subscript>2–<Emphasis Type="Italic">x</Emphasis></Subscript>Ni<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>As<Subscript>2</Subscript> Single Crystals

The vortex pinning and liquid-glass transition have been studied in BaFe_2–xNi _x As₂ single crystals with different doping levels (x = 0.065, 0.093, 0.1, 0.14, 0.18). We found that Ni-doped Ba-122 has rather narrow vortex-liquid state region. Our results show that the temperature dependence of the resistivity as well as I?V characteristics of Ni-doped Ba-122 is consistent with 3D vortex-glass model. It was found that -pinning gives the main contribution to overall pinning in 122 Ni-doped system. The vortex phase diagrams for different doping levels were built based on the obtained data of temperature of the vortex-glass transition T_g and the upper critical magnetic field H_c2.     

Raman spectroscopy of SrB<Subscript>4</Subscript>O<Subscript>7</Subscript> single crystals in the temperature range 300–1273 K

The polarized Raman spectra of SrB₄O₇ (SBO) single crystals are studied in detail in the temperature range of 300–1273 K. The TO, LO, and IO phonon lines of A₁, A₂, B₁, and B₂ symmetries of rhombic SBO at 300 K are identified. The behavior of the Raman spectra of SBO crystals is studied upon heating up to their melting. The relation of Raman spectra with the structure of boron–oxygen fragments, as well as the transformation of spectra in the process of melting of SBO crystals, is discussed.     

Thermodynamic study of compounds of the Nd-Ba-Cu-O system

Standard enthalpies of formation for solid solutions of composition Nd_{1 + x} Ba_{2 ? x} Cu₃O _y (x = 0–0.8, y = 6.65–7.24) from oxides were determined by solution calorimetry. The heat capacity of NdBa₂Cu₃O_6.87 phase was measured in the range 5–320 K by low-temperature adiabatic calorimetry. The absolute entropy S ^o(T), the difference of enthalpies H ^o(T)-H ^o(0 K), and the reduced Gibbs energy Φ^o(T) = S ^o(T)–[H ^o(T)–H ^o(0)]/T were calculated on the basis of smoothed dependence C _p (T) in the 0–320 K range. An assessment was made for the heat capacities and the absolute entropies of solid solutions Nd_1+x Ba_2?x Cu₃O _y . The obtained set of thermodynamic parameters can be used for the calculation of phase equilibria in the Nd-Ba-Cu-O system.