Local structure of disordered PbSc<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> in the region of the diffuse tetragonal phase-rhombohedral phase transition

The local structure of the ferroelectric-relaxor PbSc_1/2Nb_1/2O₃ in the temperature range from 550 to 220 K has been investigated using ⁴⁵Sc nuclear magnetic resonance. It has been found that, in the paraelectric phase at temperatures below 550 K, the crystal consists of regions of an ordered elpasolite structure and inclusions of the disordered tetragonal perovskite phase with displacements along directions of the [001] type. The relative weight of the tetragonal structure in the region of the paraelectric phase is approximately equal to 0.28. Below the temperature of the phase transition from the disordered modification to the polar phase, the relative weight of the tetragonal phase decreases with decreasing temperature. The tetragonal structure is replaced by the trigonal polar structure. In a wide temperature range (∼50 K), there exists a heterophase structure that is characteristic of relaxors. Note that the correlation length of displacements in the tetragonal phase should be very small to explain the absence of indications of the existence of this phase in the diffraction data.     

Preparation,Structure, and Dielectric and Magnetic Properties of SrFe<Subscript>2/3</Subscript>W<Subscript>1/3</Subscript>O<Subscript>3</Subscript> Ceramics

Polycrystalline samples of SrFe_2/3W_1/3O₃ (SFWO) ceramic were obtained by solid-phase reactions with subsequent sintering using conventional ceramic technology. X-ray diffraction analysis showed that at room temperature, the SFWO ceramic is single-phase and has a perovskite-type structure with tetragonal symmetry and parameters a = 3.941(9) Å, c = 3.955(6) Å, and c/a = 1.0035. In studying the magnetic properties and the Mössbauer effect in SFWO ceramics, it is found that the material is a ferrimagnet, and the iron ions are only in the valence state of Fe³⁺. It is suggested that in the temperature range of T = 150–210°C, a smeared phase transition from a cubic (paraelectric) phase to a tetragonal (ferroelectric) phase takes place in SFWO with decreasing temperature.     

Structural,magnetic, and magnetothermal properties of the Tb<Subscript>0.3</Subscript>Dy<Subscript>0.7</Subscript>Co<Subscript>2</Subscript> compound

A complex investigation of the structural, magnetic, and magnetothermal properties of the Tb_0.3Dy_0.7Co₂ compound synthesized with the use of high-purity rare-earth metals has been performed. The phase composition has been controlled using the X-ray structural analysis, and the topology of the alloy surface has been investigated using atomic-force microscopy. It has been established that the Tb_0.3Dy_0.7Co₂ compound is single-phase, while the samples selected for measurements possess a clearly pronounced texture. The magnetization has been measured using a vibrating-sample magnetometer in the fields up to 100 kOe in a temperature range from 4.2 to 200 K. The Curie temperature of the compound is 170 K. The data on the temperature dependence of heat capacity of Tb_0.3Dy_0.7Co₂ have been obtained. The magnetocaloric effect ΔT has been measured by a direct method in the fields up to 18 kOe applied both along and perpendicularly to the texture axis. The anisotropic behavior of the magnitude ΔT for this compound, which possesses the cubic structure, has been found. The maximum value of the magnetocaloric effect ΔT = 2.3 K (ΔH = 18 kOe) has been observed upon applying the magnetic field along the texture axis.     

The structural properties of RbMnX<Subscript>3</Subscript> (X = F,Cl, Br) halides

The results of nonempirical calculation of energies of three polytypes (cubic, two-layer hexagonal, and six-layer hexagonal) are given for RbMnX₃ (X = F, Cl, Br) crystals. The calculation is performed using an ionic crystal model with regard for the deformability and the dipole and quadrupole polarizabilities of ions. The behavior of these crystals under the action of hydrostatic pressure is studied. It is demonstrated that, at normal pressure, the RbMnCl₃ and RbMnBr₃ crystals have a six-layer hexagonal structure. At pressures above 11 kbar, RbMnCl₃ passes to a phase with a cubic structure; RbMnBr₃ at pressures above 90 kbar passes to a phase with a two-layer hexagonal structure. The RbMnF₃ crystal under normal conditions has a cubic structure and experiences no phase transformations under the effect of pressure. The obtained results are in satisfactory agreement with the known experimental data.     

Magnetic and structural anomalies of Na<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>C<Subscript>60</Subscript> (n = 2, 3)

Sodium fullerides Na _n C60 (n = 2, 3) have been synthesized by a liquid phase reaction and investigated with X-ray diffraction (XRD), nuclear magnetic resonance (NMR), electron paramagnetic resonance, and differential thermal analysis. XRD data indicate that the crystal structure of Na₂C₆₀ at 300 K is face centered cubic (FCC). A phase transition from primitive cubic to FCC crystal structure has been observed in this work in Na₂C₆₀ fulleride at 290 K. The transition is accompanied by the step-like change of paramagnetic susceptibility. The crystal structure of Na₃C₆₀ is more complicated than, and different from, what has been reported in the literature. A nearly seven-fold increase of paramagnetic susceptibility with increasing temperature has been observed in the Na₃C₆₀ fulleride at 240–260 K. In the same temperature range, a new line at about 255 ppm appears in the ²³Na NMR spectrum, indicating a significant increase of electron density near the Na nucleus. The observed effect can be explained by a metal-insulator transition caused by a structural transition.     

An inhomogeneously distorted state of the crystal structure of a Zn<Subscript>0.95</Subscript>Fe<Subscript>0.05</Subscript>Se cubic crystal

The structural state of a bulk Zn_0.95Fe_0.05Se cubic crystal grown by the chemical transport method from the gas phase has been investigated using thermal neutron diffraction at room temperature. It has been found that the measured neutron diffraction patterns of the crystal, in addition to structural Bragg peaks, contain a clearly identified system of superstructure reflections with the wave vector k = (1/3 1/3 1/3)2π/a (where a is the parameter of the cubic unit cell), which is interpreted as a clear evidence of the incipient transition state preceding the concentration phase transformation fcc ? hcp. It has been shown that the resulting structural state includes an inhomogeneous microstrain field with the possible appearance of long-wavelength modulations based on the initial sphalerite structure.     

Fine structure and magnetism of the cubic oxide compound Ni<Subscript>0.3</Subscript>Zn<Subscript>0.7</Subscript>O

The fine structure and spin system of the cubic oxide Ni_0.3Zn_0.7O compound prepared from the initial hexagonal phase by quenching a sample with a high temperature and applying an external hydrostatic pressure to it have been studied using magnetic measurements, synchrotron and X-ray diffraction. It has been revealed that the diffraction patterns of this compound contain a system of weak diffuse maxima with the wave vectors q = (1/6 1/6 1/6)2π/a and (1/3 1/3 1/3)2π/a, along with strong Bragg peaks of the cubic phase. It has been shown that the origin of the diffuse peaks is due to longitudinal and transverse displacements of ions with respect to symmetric crystallographic directions of the {111} type. The reasons for the ion displacement and specific features of the structure of the spin system of the strongly correlated oxide Ni_0.3Zn_0.7O compound have been briefly discussed.     

Thermodynamic properties and structure of oxyfluorides Rb<Subscript>2</Subscript>KMoO<Subscript>3</Subscript>F<Subscript>3</Subscript> and K<Subscript>2</Subscript>NaMoO<Subscript>3</Subscript>F<Subscript>3</Subscript>

According to the results of calorimetric and structural studies, the Fm{ie1202-1}m phase in K₂NaMoO₃F₃ remains stable at least to 100 K. No ferroelectric transformation assumed earlier has been revealed in a series of Rb₂KMoO₃F₃ samples prepared using various technologies. Only a phase transition of nonferroelectric origin has been observed near 195 K, and its thermodynamic characteristics have been determined. An analysis of the stability of the cubic structure of molybdenum fluorine-oxygen elpasolites-cryolites has been performed in the framework of the hypothesis on strengths of interatomic bonds. The barocaloric effect in Rb₂KMoO₃F₃ has been estimated.     

Electronic absorption spectrum of Cs<Subscript>2</Subscript>ZnI<Subscript>4</Subscript> thin films

The absorption spectrum of Cs₂ZnI₄ thin films in the energy range 3–6 eV at temperatures from 90 to 340 K has been investigated. It is established that this compound belongs to direct-gap insulators. Low-frequency exciton excitations are localized in ZnI₄ structural elements of the lattice. Phase transitions at 280 K (paraelectric phase ? incommensurate phase), 135 K (incommensurate phase ? monoclinic ferroelastic phase), and 96 K (monoclinic phase ? triclinic ferroelastic phase) have been found from the temperature dependences of the spectral position and halfwidth of the low-frequency exciton band. Additional broadening of the exciton band is observed for ferroelastic phases; it is likely to be due to exciton scattering from strain fluctuations near domain walls.     

High-pressure effect on the ferroelectric-paraelectric transition in PbTiO<Subscript>3</Subscript>

The crystal structure of lead titanate PbTiO₃ was investigated by energy dispersive X-ray diffraction at high pressures up to 4 GPa in a temperature range of 300–950 K. At the ambient conditions, the PbTiO₃ structure is tetragonal with the space group P4mm (ferroelectric phase). A structural phase transition into the cubic phase with a space group Pm[`3]mPm\bar 3m is observed at T = 747 K. It was found that the phase transition temperature decreases upon applying the high pressure with the coefficient dT _C /dP = -65 K/GPa. Dependences of parameters and volume of the unit cell on the pressure and temperature was found, and the bulk modulus and thermal expansion coefficients for the tetragonal and cubic phases of lead titanate have been calculated.     

The state of the components in Cu-CeO<Subscript>2</Subscript>-ZrO<Subscript>2</Subscript> catalysts for selective oxidation of CO

Cu-CeO₂ catalysts deposited on a commercial ZrO₂ support have been investigated. The catalyst composition has been optimized: the optimum copper content was found to be 5–10 wt % at a cerium oxide content of 23 wt %. The catalysts were investigated by X-ray diffraction analysis and X-ray photoelectron spectroscopy. According to the X-ray diffraction data, the support consists of the monoclinic ZrO₂ phase and cubic CeO₂ phase with an enlarged lattice parameter, while the catalysts contain CuO. The X-ray photoelectron data indicate the presence of a highly dispersed CuO₂ phase interacting with cerium oxide and zirconia on the surface of the catalyst having the optimum copper content.     

Phase transitions in the (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>NbOF<Subscript>5</Subscript> oxyfluoride

The thermal and dielectric properties of the (NH₄)₂NbOF₅ oxyfluoride have been investigated. It has been established that the structural phase transitions Cmc2₁ → C2 → Ia observed at the temperatures T ₁ = 258.0 K and T ₂ = 218.9 K exhibit a nonferroelectric nature. The hydrostatic pressure, which stabilizes the initial phase and destabilizes the low-temperature phase, hardly affects the temperature range of stability of the intermediate phase. The model of sequential ordering of the structural elements due to phase transitions has been analyzed using experimental data on the entropies of the phase transitions.     

Magneto-optical investigations of the domain structure and magnetization of the ferrite-garnet Tb<Subscript>0.2</Subscript>Y<Subscript>2.8</Subscript>Fe<Subscript>5</Subscript>O<Subscript>12</Subscript> in the temperature range of the spontaneous spin-reorientation phase transition

The transformation of a domain structure and technical magnetization of the Tb_0.2Y_2.8Fe₅O₁₂ single crystal in the temperature range of the spontaneous orientational phase transition have been investigated by the magneto-optical method. It has been shown that the phase transition is extended in a certain temperature range in which domains of the low-temperature and high-temperature magnetic phases coexist. It has been found that the evolution of the domain configuration in the temperature range of spin reorientation substantially depends on the presence of mechanical stresses in the crystal. Anomalies in the temperature dependences of the coercivity and magneto-optical susceptibility of the crystal due to the transformation of its domain structure during the phase transition have been revealed. The experimental results have been interpreted within the existing theory of orientational phase transitions in cubic crystals.     

Influence of deformation on the structural transformation of the Pd<Subscript>40</Subscript>Ni<Subscript>40</Subscript>P<Subscript>20</Subscript> amorphous phase

The influence of plastic deformation on the structure of the Pd₄₀Ni₄₀P₂₀ amorphous alloy has been investigated using X-ray diffraction and measurements of the velocity of sound. It has been revealed that the rolling of the sample leads to a change in the structure of the amorphous phase (distortion of the first coordination sphere) and that the structural transformations are more pronounced in the near-surface region of the sample. The rolling also results in a decrease in the transverse velocity of sound. The observed effects decrease with time. It has been demonstrated that the revealed effects are associated with the inelastic deformation of the amorphous alloy.     

Structural changes during phase transitions and the critical and noncritical order parameters in the (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>Nb(O<Subscript>2</Subscript>)<Subscript>2</Subscript>F<Subscript>4</Subscript> crystal

The structures of two phases of the (NH₄)₃Nb(O₂)₂F₄ crystal, namely, the parent cubic phase and the most distorted low-temperature phase, have been determined from data of an X-ray diffraction experiment performed for a powder sample. The profile and structural parameters have been refined according to the procedure implemented in the DDM program. The results obtained have been discussed with invoking the group-theoretical analysis of the complete order parameter condensate, which takes into account the critical and noncritical atomic displacements and allows the interpretation of the obtained experimental data. It has been found that the most probable sequence of structural transformations occurring in the crystal can be schematically represented in the following form:

V<Subscript>52</Subscript>O<Subscript>64</Subscript> tetragonal superstructure of cubic vanadium monoxide with vacancies in the metal sublattice

The atom-vacancy ordering of cubic vanadium monoxide VO_1.29, which has basis cubic structure B1 and structural vacancies in the metal sublattice, has been studied using the x-ray diffraction method. It has been shown that the formation of the tetragonal (space group I4₁/amd) ordered phase V₅₂O₆₄ of cubic vanadium monoxide VO_y proceeds as a first-order phase transition through the disorder-order channel including 22 nonequivalent superstructure vectors of four stars {k ₁₀}, {k ₄}, {k ₃}, and {k ₂}. The distribution function of the vanadium atoms in the V₅₂O₆₄ tetragonal superstructure has been calculated.     

Magnetism of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> manganite in structurally ordered and disordered states

The specific features of the crystal structure and the magnetic state of stoichiometric lithium manganite in the structurally ordered Li[Mn₂]O₄ and disordered Li_{1 − δ}Mn_δ[Mn_{2 − δ}Li_δ]O₄ (δ = 1/6) states have been investigated using neutron diffraction, X-ray diffraction, and magnetic methods. The structurally disordered state of the manganite was achieved under irradiation by fast neutrons (E _eff ≥ 1 MeV) with a fluence of 2 × 10²⁰ cm⁻² at a temperature of 340 K. It has been demonstrated that, in the initial sample, the charge ordering of manganese ions of different valences arises at room temperature, which is accompanied by orthorhombic distortions of the cubic spinel structure, and the long-range antiferromagnetic order with the wave vector k = 2π/c(0, 0, 0.44) is observed at low temperatures. It has been established that the structural disordering leads to radical changes in the structural and magnetic states of the LiMn₂O₄ manganite. The charge ordering is destroyed, and the structure retains the cubic symmetry even at a temperature of 5 K. The antiferromagnetic type of ordering transforms into ferrimagnetic ordering with local spin deviations in the octahedral sublattice due to the appearance of intersublattice exchange interactions.     

Quasi-two-dimensional ferroelectricity in KNbO<Subscript>3</Subscript>/KTaO<Subscript>3</Subscript> superlattices

First-principles density functional theory is used to calculate the phonon spectrum in the paraelectric phase, the ground-state structure and polarization distribution in the polar phase, and energies of ferro- and antiferroelectrically ordered phases of free-standing (KNbO₃)₁(KTaO₃) _n ferroelectric superlattices with n = 1–7. It is established that quasi-two-dimensional ferroelectricity with polarization oriented in the layer plane, which weakly interacts with polarization in neighboring layers, appears in potassium niobate layers with a thickness of one unit cell in the superlattices. The possibility of using of such ferroelectric superlattices as a medium for three-dimensional information recording is shown.     

Synthesis,crystal structure,Hirshfeld surface analysis,and vibrational and DFT investigation of [C<Subscript>6</Subscript>H<Subscript>10</Subscript>(NH<Subscript>3</Subscript>)<Subscript>2</Subscript>]<Subscript>3</Subscript>CuBr<Subscript>4</Subscript>.3Br

Single crystal of a new organic–inorganic hybrid material [C₆H₁₀(NH₃)₂]₃CuBr₄.3Br was synthesized by the slow evaporation method at room temperature and characterized by X-ray diffraction, FTIR, Raman spectroscopy, UV–Vis, dielectric measurements, and Hirschfield surface analysis. The title compound crystallizes in trigonal system \( P\overline{3} \).The crystal packing is governed by the N-H…Br and non-classical C-H…Br hydrogen-bonding interactions between the 1, 2-diamoniumcyclohexane cations, the tetrahedral [CuBr₄]^3? anions, and the isolated ion Br^?. Theoretical calculations were performed using density functional theory (DFT) for studying the molecular structure, vibrational spectra, and optical properties of the investigated molecule in the ground state. The optimized geometrical parameters obtained by DFT calculations are in good agreement with single crystal XRD data. The optical properties were investigated by optical absorption and show two bands at 260 and 305 nm.