Calculation of refractive indices for the (NH<Subscript>2</Subscript>CH<Subscript>2</Subscript>COOH)<Subscript>2</Subscript> · HNO<Subscript>3</Subscript> crystal

The refraction R of the diglycine nitrate (DGN) crystal, (NH₂CH₂COOH)₂ · HNO₃, in the para-and ferroelectric phases has been calculated in the model of noninteracting diatomic chemical bonds of the elementary unit cell of the crystal on the basis of the longitudinal and transversal polarizabilities of these bonds. The calculated magnitudes of the principal refractive indices n _p , n _m , and n _g and the orientations of the optical indicatrix of the crystal agree satisfactorily with experimentally observed values. Introducing the coefficient of Lorenz-Lorentz interaction x into the corresponding formula permits better agreement of the calculated and experimental refractive indices of DGN crystal to be obtained. The temperature changes of these x coefficients upon the ferroelectric phase transition in the DGN crystal have been analyzed.     

O<Subscript>2</Subscript> photodesorption from AuO<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> and Au<Subscript>2</Subscript>O<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack>

Using time-resolved photoelectron spectroscopy, the decay channels of AuO₂⁻ and Au₂O₂⁻ following photoexcitation with 3.1-eV photons have been studied. For AuO₂⁻, a state with a rather long lifetime of 30 ps has been identified. Its decay path could not be determined but photodesorption can be excluded. For Au₂O₂⁻, the spectra indicate O₂ desorption after 3.1-eV photoexcitation on a time scale of 1 ps. While comparing these results on Au _n O₂⁻ with analogous data on Ag _n O₂⁻ clusters, a discernible pattern emerges: for dissociatively bound O₂(AuO₂⁻, Ag₃O₂⁻), there are long-living excited states which do not decay by oxygen desorption, while for molecular chemisorption (Au₂O₂⁻, Ag₂O₂⁻, Ag₄O₂⁻, Ag₈O₂⁻), the 3.1-eV photoexcitation triggers fast O₂ desorption with a high quantum yield.     

High-Temperature Heat Capacity of Zn<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript>–Cu<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript> Solid Solutions

Differential scanning calorimetry has been used to study the influence of temperature on the heat capacity of synthesized vanadates Zn₂V₂O₇, (Cu_0.56Zn_1.44)V₂O₇, and (Cu_1.0Zn_1.0)V₂O₇. It is found that dependences C_p = f(T) have extremes. The thermodynamic properties of Zn₂V₂O₇ have been determined.     

Effect of γ irradiation on the thermochromic phase transition in [(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>2</Subscript>NH<Subscript>2</Subscript>]<Subscript>2</Subscript>CuCl<Subscript>4</Subscript> crystals (as derived from heat capacity measurements)

The heat capacity of [(C₂H₅)₂NH₂]₂CuCl₄ crystals, both nonirradiated and γ-irradiated to a dose of 10⁷R, was studied in the temperature interval 90–330 K by adiabatic calorimetry. The temperature dependence of C_p(T) was found to have a peak-shaped anomaly in the region of the thermochromic phase transition (PT) at T = 322.7 K. Smoothened experimental heat capacity data were used to calculate the changes in the thermodynamic functions. The changes in the entropy and enthalpy of the thermochromic PT were determined to be ΔS = 42 J K^?1 mol^?1 and ΔH = 13653 J mol^?1 for the nonirradiated crystals and ΔS = 39 J K^?1 mol^?1 and ΔH = 12120 J mol^?1 for the irradiated crystals, respectively. Irradiation of a [(C₂H₅)₂NH₂]₂CuCl₄ crystal by γ rays to a dose of 10⁷ R was shown to shift the PT point toward lower temperatures by ΔT ≈ 1.7 K.     

Preparation and characterization of organic–inorganic hybrid compound [N(C<Subscript>4</Subscript>H<Subscript>9</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>Cu<Subscript>2</Subscript>Cl<Subscript>6</Subscript>

Organic–inorganic hybrid sample [N(C₄H₉)₄]₂Cu₂Cl₆ was prepared via the reaction between copper chloride and tetrabutylammonium chloride. The compound was characterized by X-ray powder diffraction, IR, Raman, differential scanning calorimetry (DSC), DTA-TGA analysis and electrical impedance spectroscopy. DSC studies indicate a presence of one-phase transition at 343 K. The complex impedance of compound [N(C₄H₉)₄]₂Cu₂Cl₆ have been investigated in temperature and frequency ranges 300–380 K and 200 Hz–5 MHz, respectively. The Z′ and Z″ versus frequency plots are well fitted to an equivalent circuit model. The circuits consist of the parallel combination of bulk resistance R _p and constant phase elements CPE. The frequency dependence of the conductivity is interpreted in term of Jonscher's law: s(w) = s_dc + Awⁿ \sigma (\omega ){ } = {\sigma_{\rm{dc}}} + { }A{\omega^n} . The conductivity follows the Arrhenius relation. The variation of the value of these elements with temperatures confirmed the availability of the phase transition at 343 K detected by DSC and electrical measurements.     

Magnetic and magnetoresistive properties of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sr<Subscript>2</Subscript>FeMoO<Subscript>6–δ</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoheterostructures

A method has been developed for fabricating nanoporous matrices based on anodic aluminum oxide for the deposition of ferromagnetic nanoparticles in them. The modes of deposition of strontium ferromolybdate thin films prepared by the ion-plasma method have been worked out, and the magnetic and magnetoresistive properties, structure, and composition of the films have been investigated. It has been revealed that the microstructure and properties of the strontium ferromolybdate films deposited by ionplasma sputtering depend on the deposition rate and the temperature of the substrate. Based on the measurement of the electrical resistivity of nanoheterostructures in a magnetic field, it has been found that the magnetoresistance reaches 14% at T = 15 K and B = 8 T, which is due to the manifestation of tunneling magnetoresistance.     

Temperature dependence of the quenching of N<Subscript>2</Subscript> (C <Superscript>3</Superscript>Π<Subscript>u</Subscript>) by N<Subscript>2</Subscript> (X) and O<Subscript>2</Subscript> (X)

The temperature dependences of the quenching rate constants of the states N₂ (${\rm C} \ {^{3}{ \rm \Pi }_{u}}${\rm C} \ {^{3}{ \rm \Pi }_{u}} v^′=0,1) by N₂ (X) and of the state N₂ (${\rm C} \ {^{3}{ \rm \Pi }_{u}} \ v^{\prime}=0${\rm C} \ {^{3}{ \rm \Pi }_{u}} \ v^{\prime}=0) by O₂ (X) are studied. Time-resolved light emission from the gas was analyzed in the temperature range from 300 K to 210 K keeping the gas at constant density. In case of quenching by N₂ (X), the quenching rate constant for the vibrational level v^′= 0 increases by (13 ±3)% with gas cooling whereas the quenching rate constant for v^′= 1 decreases by (5.0 ±2.5)% in this temperature range. For quenching by O₂ (X), the quenching rate constant decreases by (3 ±2)% with gas cooling. The temperature variation of the N₂ (C ³Π_u v^′=0) emission intensity for pure nitrogen and dry air are calculated using the obtained quenching rate constants and is compared with the experimental data available in the literature.     

Elastic properties of TeO<Subscript>2</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–Ag<Subscript>2</Subscript>O glasses

A series of glasses [(TeO₂) _x (B₂O₃)_1−x ]_1−y [Ag₂O] _y with x = 70 and y = 10, 15, 20, 25 and 30 mol% were synthesised by rapid quenching. Longitudinal and shear ultrasonic velocity were measured at room temperature and at 5 MHz frequency. Elastic properties, Poisson's ratio, microhardness, softening temperature and Debye temperature have been calculated from the measured density and ultrasonic velocity at room temperature. The experimental results indicate that the elastic constants depend upon the composition of the glasses and the role of the Ag₂O inside the glass network is discussed. Estimated parameters based on Makishima–Mackenzie theory and bond compression model were calculated in order to analyse the experimental elastic moduli. Comparison between the experimental elastic moduli data obtained in the study and the calculated theoretically by the mentioned above models has been discussed.     

μSR study of Eu<Subscript>0.8</Subscript>Ce<Subscript>0.2</Subscript>Mn<Subscript>2</Subscript>O<Subscript>5</Subscript> and EuMn<Subscript>2</Subscript>O<Subscript>5</Subscript> multiferroics

A comparative μSR study of ceramic samples of the EuMn₂O₅ and Eu_0.8Ce_0.2Mn₂O₅ multiferroics is performed in the temperature range from 15 to 300 K. It is found that the Ce doping of the EuMn₂O₅ sample slightly reduces the temperature of the magnetic phase transition from T _N = 45 K for the EuMn₂O₅ sample to T _N = 42.5 K for the Eu_0.8Ce_0.2Mn₂O₅ sample. Below the temperature T _N for both samples, there are two types of localization of a thermalized muon with different temperature dependences of the precession frequency of the magnetic moment of the muon in an internal magnetic field. The higher frequency in both samples refers to the initial antiferromagnetic matrix. The behavior of this frequency in Eu_0.8Ce_0.2Mn₂O₅ follows the Curie–Weiss law with the exponent β = 0.29 ± 0.02, which differs from the value β = 0.39 standard for 3D Heisenberg magnetics and is observed in EuMn₂O₅, because of the strong frustration of the doped sample. The temperature-independent low frequency is due to the presence of Mn³⁺–Mn⁴⁺ ferromagnetic pairs located along the b axis of the antiferromagnetic matrix and in the regions of phase separation, which contain such ion pairs and e _g electrons recharging them. In both samples, polarization losses are the same (about 20%) and are associated with the formation of Mn⁴⁺–Mn⁴⁺ + Mu complexes near Mn³⁺–Mn⁴⁺ ferromagnetic pairs. In the temperature interval from 25 to 45 K, the separation of the Eu_0.8Ce_0.2Mn₂O₅ structure into two fractions where the relaxation rates of polarization of muons differ by an order of magnitude is revealed. This effect is due to a change in the state of regions of phase separation (1D superlattices) at the indicated temperatures. Such effect in EuMn₂O₅ is significantly weaker.     

Cluster spin glass and superparamagnetism in RuSr<Subscript>2</Subscript>Eu<Subscript>1.5</Subscript>Ce<Subscript>0.5</Subscript>Cu<Subscript>2</Subscript>O<Subscript>10-</Subscript><Subscript>δ</Subscript>

We investigate in detail the dc magnetization and nonlinear ac susceptibility behavior of the superconducting ferromagnet RuSr₂Eu_1.5Ce_0.5Cu₂O_{10- δ} (Ru1222) to develop a comprehensive understanding of the spin glass and superparamagnetism in this material. The structural properties of the system result in the formation of magnetic (ferromagnetic) clusters of different sizes, shapes and properties. The magnetic clustering of the system leads to observation of various features in dc magnetization and ac susceptibility consistent with superparamagnetism and cluster spin glass states, which can coexist or stand alone, depending on the temperature range considered. Experimental results of magnetic measurements in combination with their analysis have enabled us to explain and distinguish these phenomena, as well as to propose a temperature dependent scenario of the system behavior.     

Specific heat of the [NH<Subscript>2</Subscript>(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>]<Subscript>2</Subscript>ZnCl<Subscript>4</Subscript> crystal in the temperature region 80–300 K

The specific heat of [NH₂(CH₃)₂]₂ZnCl₄ was measured calorimetrically in the temperature region 80–300 K. As the temperature T decreases, the C _p (T) dependence indicates a phase transition sequence, with the phase transition at T₆=151 K observed for the first time. The thermodynamic characteristics of the crystal were refined. The transformation occurring at T₂=298.3 K is shown to be an incommensurate-commensurate phase transition.     

Hydrogen bond and exchange interaction in the (CuSO<Subscript>4</Subscript>)(en)·2H<Subscript>2</Subscript>O and (CuSO<Subscript>4</Subscript>)(en)·2D<Subscript>2</Subscript>O organometallic compounds

The influence of the replacement of hydrogen with deuterium in molecules of water of crystallization in the structure of the (CuSO₄)(en) · 2H₂O and (CuSO₄)(en)·2D₂O organometallic compound molecules on exchange interaction between copper ions was studied. The X-ray structural data and the data on angular anisotropy of the effective g-factor of Cu²⁺ ions in both compounds show that distortions of the initial structure caused by deuteration are minimum. A comparative analysis of the width of the exchange coupled EPR lines of the two compounds is indicative of a decrease in the exchange parameter in the deuterated sample, which substantiates the participation of H-bonds in exchange interactions in the systems studied.     

“Negative” gap in the spectrum of localized states of (In<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>0.9</Subscript>(SrO)<Subscript>0.1</Subscript>

The reflection R(?ω), transmission t(?ω), absorption α(?ω), and refraction n(?ω) spectra of polycrystalline In₂O₃–SrO samples with low optical transparency, which contain In₂O₃ and In₂SrO₄ crystallites with In₄SrO_{6 + δ} interlayers, are examined. In the region of small ?ω values, the reflection coefficient decreases as the resistance of samples saturated with oxygen increases. Spectral dependences n(?ω) and α(?ω) are calculated using the classical electrodynamics relations. The results are compared to the data based on the t(?ω) spectra. The calculated absorption spectra are interpreted within the model with an overlap of tails of the density of states in the valence band and in the conduction band. A “negative” gap E _gn in the density of states with a width from–0.12 to–0.47 eV is formed in highly disordered samples in this model. It is demonstrated that the high density of defects and the band of deep acceptor states of strontium in the major matrix In₂O₃ phase are crucial to tailing of the absorption edge and its shift toward lower energies. The direct gap E _gd = 1.3 eV corresponding to the In₂SrO₄ phase is determined. The energy band diagram and the contribution of tunneling, which reduces the threshold energy for interband optical transitions, are discussed.     

Electrical switching in the MoO<Subscript>3</Subscript>–WO<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> and MoO<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

High field electrical switching on blown films of MoO₃(60%)–P₂O₅(40%), MoO₃(50%)–WO₃(10%)–P₂O₅(40%), and MoO₃(45%)–WO₃(15%)–P₂O₅(40%) having different thicknesses was studied and compared. Switching was observed using two terminal samples. S-type current–voltage characteristic (current-controlled negative resistance—CCNR) with memory was observed in molybdenum–phosphate glasses, but N-type characteristic (voltage-controlled negative resistance—VCNR) with threshold in tungsten–molybdenum–phosphate glasses was observed. The important observation was that with the addition of WO₃ to binary MoO₃–P₂O5 led to a change of I–V characteristic from CCNR with memory to VCNR with threshold. The measurements of density and molar volume showed linear relation between MoO₃ content and density which decreased with the increase of MoO₃ content. The samples’ thickness had no significant effect on threshold voltage. The attained results also indicated that the electrode material had no effect on switching property of devices. The switching behavior of the devices did not show any dependence on the polarity of the applied voltage. In terms of the effect of heat on the switching behavior of molybdenum–phosphate glasses, it was found that threshold voltage decreases with increasing of temperature. Finally, the switching phenomenon was explained by thermal (formation of crystalline filaments) and electronic models.     

Synthesis and characterization of oxide cathode materials of the system (1-x-y)LiNiO<Subscript>2</Subscript>·xLi<Subscript>2</Subscript>MnO<Subscript>3</Subscript>·yLiCoO<Subscript>2</Subscript>

Composite cathode materials produced by integrating isostructural (2D-layered) compounds LiNiO₂, LiCoO₂, and Li₂MnO₃ (Li(Li_1/3Mn_2/3)O₂) have been investigated utilizing a compositional phase diagram. The samples were characterized by multiple techniques to establish structure–property relationships. Specifically, for structural characterization, powder X-ray diffraction, scanning electron microscopy, thermo-gravimetric analysis, and X-ray photoelectron spectroscopy were carried out. For properties, electrochemical characterization was carried out. The best composition showed a discharge capacity of 244 mAh/g (C/15 rate) in the testing range of 4.6–2 V, with good coulombic efficiency and cyclability.     

Heat capacity of the [N(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>CdBr<Subscript>4</Subscript> crystal in the temperature range 80–300 K

The heat capacity of the [[N(C₂H₅)₄]₂CdBr₄ crystal is measured by the calorimetric method in the temperature range from 80 to 300 K. It is revealed for the first time that the temperature dependence of the heat capacity C _p (T) exhibits an anomaly associated with the first-order phase transition occurring at the temperature T ₁ = 226.5 K. A long relaxation of the temperature of the crystal is observed in the temperature range 150–165 K.     

Atomistic simulation of sodium–gadolinium molybdate of stoichiometric (Na<Subscript>1/2</Subscript>Gd<Subscript>1/2</Subscript>MoO<Subscript>4</Subscript>) and cation-deficient (Na<Subscript>2/7</Subscript>Gd<Subscript>4/7</Subscript>MoO<Subscript>4</Subscript>) compositions

Crystals of sodium–gadolinium molybdates of two compositions: stoichiometric (Na_1/2Gd_1/2MoO₄) and cation-deficient (Na_2/7Gd_4/7MoO₄) composition in which 1/7 of the corresponding cation positions are not occupied are simulated by the method of interatomic potentials. For cation-deficient crystals, two kinds of cation position distribution are considered: the statistical distribution of sodium, gadolinium, and unoccupied cation positions in the I4₁/a structure and their partial ordering in the I space group. As a result of the simulation, structural characteristics of sodium–gadolinium molybdates agreeing well with the known experimental data are obtained. In addition, a number of important elastic and thermodynamic properties of these compounds are predicted. The results obtained in the partial-occupancy approximation and by constructing a 7 × 2 × 2 supercell are compared. The local structure of sodium–gadolinium molybdates are analyzed in detail. The influence of the deviation from the stoichiometry as well as cation ordering on the properties of these crystals is discussed.     

Long-range magnetic order in copper nitrate monohydrate Cu(NO<Subscript>3</Subscript>)<Subscript>2</Subscript> · H<Subscript>2</Subscript>O

The magnetic phase diagram of copper nitrate monohydrate Cu(NO₃)₂ · H₂O and the basic parameters of its magnetic subsystem have been determined by measuring the thermodynamic properties of this compound. This compound becomes antiferromagnetically ordered at T _N = 3.6 K, undergoes the spin-flop and spin-flip transitions at H _C1 ～ 0.06 T and H _C2 ～ 1.1 T, respectively, at low temperatures. The magnetization of Cu(NO₃)₂ · H₂O at T _SR = 2.7 K exhibits an additional anomaly, which is likely attributed to the spin-reorientation transition.     

Superconductivity at normal pressure in κ-(BEDT-TTF)<Subscript>2</Subscript>Cu[N(CN)<Subscript>2</Subscript>]Cl crystals

Single crystals of the κ-(BEDT-TTF)₂Cu[N(CN)₂]Cl cation-radical salt are obtained. These crystals exhibit metallic properties and pass to a superconducting state with T_c = 11.5 K at ambient pressure.