Effect of ionizing radiation on the dielectric characteristics of TlInSe<Subscript>2</Subscript> and TlGaTe<Subscript>2</Subscript> single crystals

The temperature dependences of the electrical conductivity and the permittivity of TlInSe₂ and TlGaTe₂ crystals unirradiated and irradiated with 4-MeV electrons at a doze of 10¹⁶ cm⁻² have been investigated. It has been established that electron irradiation leads to a decrease in the electrical conductivity σ and the permittivity ɛ over the entire temperature range under study (90–320 K). It has been revealed that the TlInSe₂ and TlGaTe₂ single crystals undergo a sequence of phase transitions characteristic of crystals of this type, which manifest themselves as anomalies in the temperature dependences σ = f(T) and ɛ = f(T). Electron irradiation at a doze of 10¹⁶ cm⁻² does not affect the phase transition temperatures of the crystals under investigation.     

Nanoclusters in mixed crystals Hg<Subscript>2</Subscript><Emphasis Type="Italic">Hal</Emphasis><Subscript>2</Subscript>

The Raman spectra of mixed Hg₂(Br,I)₂ and Hg₂(Cl,Br)₂ crystals were investigated. The multimode behavior of optical vibrations induced by presence of three types of molecules (Hg₂ Hal′₂, Hg₂ Hal″₂ and Hg₂ Hal′Hal″) in the crystals was observed experimentally and is discussed theoretically. Phase transition effects such as soft modes, density of states, IR vibration branches, and anti- and ferroelectric nanoclusters induced by polar Hal′-Hg-Hg-Hal″ molecules and their immediate environment, were observed in the Raman spectra.     

Muon-spin-relaxation investigation of EuMn<Subscript>2</Subscript>O<Subscript>5</Subscript>

The magnetic properties of the EuMn₂O₅ multiferroic (samples consisting of single crystals and ceramic samples) have been investigated by the muon-spin-relaxation (μSR) method in the temperature range of 10–300 K. Below the magnetic ordering temperature T _N = 40 K, the loss of the polarization of muons and the effect of the external magnetic field have been observed. Both phenomena can be explained by an additional channel of the depolarization of muons owing to the appearance of muons in a medium with a low electron density due to the charge separation process (the redistribution of the electron density in the phase transition process). The “memory” phenomenon has been revealed in a sample in the external magnetic field; the memory relaxation time depends on the size of the structure units of the samples (single crystals or ceramic grains).     

Electron paramagnetic resonance of spin-variable metallomesogens [Fe<Emphasis Type="Italic">L</Emphasis><Subscript>2</Subscript>]<Emphasis Type="Italic">X</Emphasis> (<Emphasis Type="Italic">X</Emphasis> = PF<Subscript>6</Subscript>, SCN)

Significant differences in the manifestation of spin-crossover properties of the mesogen compounds [FeL ₂]X with oxysalicylidene-N′-ethyl-N-ethylenediamine ligands L and anions X = PF₆⁻ and SCH⁻ have been found by means of electron paramagnetic resonance. The electron paramagnetic resonance data and the quantum-chemical calculation within the density functional theory enables us to establish that the observed specific features are associated with the incorporation of the SCH⁻ ion into the first coordination sphere of the Fe(III) ion. The role of the transition of the material to the liquid-state phase in the formation of a low-dimensional (two-dimensional) structure with stronger intermolecular interactions has been revealed.     

Temperature dependence of the order parameter and of diffuse scattering in the Hg<Subscript>2</Subscript>Cl<Subscript>2</Subscript> model ferroelastics

The fundamental and diffuse x-ray reflections from Brillouin zone-edge X points of the paraelastic phase of Hg₂Cl₂ crystals (whose integrated intensity is related to the order parameter and its fluctuations) were studied. Information was obtained on the temperature dependence of the order parameter and of diffuse scattering, and the critical exponents were determined. The conclusion is drawn that the ferroelastic phase transition in these crystals is close to the tricritical point.     

Surface impedance of <Emphasis Type="Italic">k</Emphasis>-(BEDT-TTF)<Subscript>2</Subscript>Cu[N(CN)<Subscript>2</Subscript>]Br crystals

Precision measurements of the real and imaginary parts of the microwave surface impedance Z _ac(T) = R _ac(T) + iX _ac(T) of the conducting ac layers of the k-(BEDT-TTF)₂Cu[N(CN)₂]Br crystals in the temperature interval of 0.5 < T < 100 K have demonstrated a series of features: (i) the temperature course of the field penetration depth is close to linear Δλ_ac(T)∞ΔX _ac(T) in the superconducting state at T T _c ∼ 11.5 K; (ii) the curves R _ac(T) = X _ac(T) coincide at T _c < T < 40 K; (iii) the X _ac(T) value at T > 40 K increases in comparison with R _ac(T); (iv) the dependence R _ac(T) at T > 40 K is nonmonotonic in thin crystals. These features of the impedance Z _ac(T) with increasing T are interpreted in terms of (i) the d-type symmetry of the superconducting order parameter, (ii) normal skin effect, (iii) manifestations of the antiferromagnetic fluctuations, and (iv) the size effect. The electrodynamic parameters of k-(BEDT-TTF)₂Cu[N(CN)₂]Br have been determined.     

EPR of Gd<Superscript>3+</Superscript> ion in mixed CeO<Subscript>2</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocrystals

This paper reports on the results of EPR studies of mixed CeO₂-Y₂O₃ crystals (including nanosized crystals) doped by gadolinium ions. It is revealed that the width of the line corresponding to the allowed transition 1/2 ↔ −1/2 between the Kramers-conjugated states |±1/2〉 of the Gd³⁺ ion decreases with a decrease in the powder size from macrosizes to nanosizes. The observed dependence can be due to the increase in the unit cell size during grinding of the samples.     

Long- and short-range order in the Pd<Subscript>6</Subscript>B monoclinic superstructure and M<Subscript>6</Subscript>X<Subscript>5</Subscript> and M<Subscript>6</Subscript>X allied superstructures

Symmetry analysis of the Pd₆B monoclinic superstructure (space group C2/c) formed in the cubic (with the B1 structure) solid solution of boron in palladium (PdB _y ) has been carried out. The formation of this superstructure proceeds as a first-order phase transition via the disorder-order channel including nine nonequivalent superstructure vectors of four stars {k ₁₀}, {k ₄}, {k ₃}, and {k ₀}. For the Pd₆B monoclinic super-structure (space group C2/c), the distribution function for boron atoms is calculated and the interval of admissible values of the long-range order parameters is defined. It is shown that the transition channel determined in this way coincides with the channel in which the M₆X monoclinic superstructure (space group C2) is formed; therefore, the Pd₆B superstructure can also be described in space group C2 to the same degree of accuracy. The higher symmetry of the monoclinic model (space group C2/c) suggests that it describes the structure of the Pd₆B phase (Pd₆B□₅), as well as of mutually inverse phases M₆X□₅ and M₆X₅□, more adequately than the model with space group C2. It is shown that superstructures of the M₆X□₅ type (space groups C2/c, C2, C2/m, and P3₁) and inverse superstructures of the M₆X₅□ type with the same space groups have the positions of the nearest surrounding of metal atoms by two types of nonmetallic sublattice sites located in the first and second coordination spheres.     

Phase transition effects in polycrystalline Hg<Subscript>2</Subscript>Br<Subscript>2</Subscript> samples

The effects accompanying the ferroelastic phase transition in Hg₂Br₂ polycrystalline samples are compared in an x-ray diffraction study with similar effects observed to occur in Hg₂Br₂ single crystals. In particular, an analysis is made of the “orthorhombic” splitting of the basal plane reflections and the behavior with temperature of the Bragg and diffuse reflections from the X points of the Brillouin zone, which characterize the behavior of the order parameter and its fluctuations, respectively. Polycrystalline samples exhibit strong smearing of the phase transition effects originating from the existence of damaged surface layers and elastic and plastic strain fields which induce order parameter fluctuations over a wide temperature range.     

Order parameter and its fluctuations in Hg<Subscript>2</Subscript>Br<Subscript>2</Subscript> model ferroelastics

The Bragg and diffuse reflections from different X points of the Brillouin zone boundary of the Hg₂Br₂ crystal in the paraphase are studied. The intensities of these reflections are related to the order parameter and its fluctuations. The temperature dependence of the order parameter and its fluctuations is analyzed, and the values of the critical exponents indicating closeness of the phase transition in these crystals to the tricritical point are determined.     

Evolution of MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> crystals in Al-Mg-SiO<Subscript>2</Subscript> composites

The present study analyzes the morphological transformations of reaction products i.e., MgO, MgAl₂O₄ occurring during the reaction between SiO₂ and Al-Mg alloy in Al-Mg-SiO₂ composite processed by the liquid metallurgy technique. Different phases of platelet and hexagonal morphologies are detected and their composition analysis by EDS has confirmed them as being transition phases existing between MgO, MgAl₂O₄ and Al₂O₃. This study has also revealed the gradual transformation of (i) MgO needles to octahedral MgAl₂O₄ through Mg-Al-Si-O and Mg-Al-O transition phases having platelet morphologies and (ii) MgAl₂O₄ to Al₂O₃ through hexagonal transition phases on holding of Al-5Mg-SiO₂ and Al-1Mg-SiO₂ composites respectively at 1023K. Fully developed α-Al₂O₃ crystals are not observed under the present experimental conditions, wherein the Mg content is well above the equilibrium Mg content required for the formation of stable Al₂O₃ (<0.05 wt. %). PACS 05.70.Np     

Symmetry analysis of the monoclinic Pd<Subscript>6</Subscript>B superstructure: Long- and short-range orders

A symmetry analysis of the monoclinic (space group C2/c) Pd₆B superstructure formed in the cubic (with structure B1) boron solid solution PdB _y in palladium has been performed. The formation of this superstructure occurs as a first-order phase transition via the disorder-order transition channel including nine nonequivalent superstructure vectors of four stars {k ₁₀}, {k ₄}, {k ₃}, and {k ₀}. For the monoclinic (space group C2) Pd₆B superstructure, the distribution function of boron atoms has been calculated and the interval of admissible values of long-range order parameters has been determined. It has been shown that the found transition channel is identical to the channel of the formation of the monoclinic (space group C2/c) M ₆ X superstructure; therefore, the Pd₆B superstructure can be described with the same accuracy in space group C2. The higher symmetry of the monoclinic (space group C2/c) model suggests that it more accurately describes the structure of the phase Pd₆B (Pd₆B□₅) and mutually inverse phases M ₆ X□₅ and M ₆ X ₅□ than the model with space group C2. It has been demonstrated that there are two types of the nearest environment of metal atoms with non-metal sublattice sites arranged in the first and second coordination spheres in M ₆ X□₅-type superstructures (space groups C2/c, C2, C2/m, and P3₁) and in inverse M ₆ X ₅□-type superstructures with the same space groups.     

Pseudogap behavior in Bi<Subscript>2</Subscript>Ca<Subscript>2</Subscript>SrCu<Subscript>2</Subscript>O<Subscript>8</Subscript>: Results of the generalized dynamical mean-field approach

Pseudogap phenomena are observed for the normal underdoped phase of different high-T _c cuprates. Among others, the Bi₂Sr₂CaCu₂O_{8 − δ} (Bi2212) compound is one of the most studied experimentally. To describe the pseudogap regime in Bi2212, we use a novel generalized ab initio LDA + DMFT + Σ_k hybrid scheme. This scheme is based on the strategy of one of the most powerful computational tools for real correlated materials: the local density approximation (LDA) + dynamical mean-field theory (DMFT). Conventional LDA + DMFT equations are here supplied with an additional (momentum-dependent) self-energy Σ_k in the spirit of our recently proposed DMFT + Σ_k approach taking into account pseudogap fluctuations. In the present model, Σ_k describes nonlocal correlations induced by short-range collective Heisenberg-like antiferromagnetic spin fluctuations. The effective single-impurity problem of the DMFT is solved by the numerical renormalization group (NRG) method. Material-specific model parameters for the effective x ² − y ² orbital of Cu-3d shell of the Bi2212 compound, e.g., the values of intra-and interlayer hopping integrals between different Cu sites, the local Coulomb interaction U, and the pseudogap potential Δ were obtained within the LDA and LDA + DMFT schemes. Here, we report on the theoretical LDA + DMFT + Σ_k quasiparticle band dispersion and damping, Fermi surface renormalization, momentum anisotropy of (quasi)static scattering, densities of states, spectral densities, and angular-resolved photoemission (ARPES) spectra, taking into account pseudogap and bilayer splitting effects for normal (slightly) underdoped Bi2212 (δ = 0.15). We show that LDA + DMFT + Σ_k successfully describes strong (pseudogap) scattering close to Brillouin zone boundaries. Our calculated LDA + DMFT + Σ_k Fermi surfaces and ARPES spectra in the presence of pseudogap fluctuations are almost insensitive to the bilayer splitting strength. However, our LDA-calculated value of bilayer splitting is rather small to describe the experimentally observed peak-dip-hump structure. The results obtained are in good semiquantitative agreement with various recent ARPES experiments. The article was submitted by the authors in English.     

Critical behavior of the heat capacity of the manganite La<Subscript>0.87</Subscript>K<Subscript>0.13</Subscript>MnO<Subscript>3</Subscript>

The heat capacity of the manganite La_0.87K_0.13MnO₃ has been measured in the temperature range 80–350 K. The nature of the ferromagnetic phase transition and the critical properties of heat capacity near the Curie temperature have been studied. The regularities of variations in the universal critical parameters near the phase transition point have been established. The calculated critical exponent and amplitudes of the heat capacity with allowance for corrections on the scaling (α = −0.13 and A ⁺/A ⁻ = 1.178) correspond to the critical behavior of the 3D Heizenberg model.     

Dielectric and polar order behaviors of BaTiO<Subscript>3</Subscript>-Bi(Mg<Subscript>1/2</Subscript>Ti<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> ceramics

New perovskite solid solution ceramics of (1−x)BaTiO₃-xBi(Mg_1/2Ti_1/2)O₃ ((1−x)BT-xBMT, x≤0.09) were synthesized by the solid-state reaction technique. X-ray diffraction studies have revealed a stable single perovskite structure for all samples. Dielectric measurements were carried out at different frequencies and temperatures. The polarization evolutions with temperatures were measured to investigate the ferroelectric properties. All the compositions show features of ferroelectrics with diffuse phase transition, though the temperature T _m of their dielectric constant maximum ε _m is frequency dependent. The dielectric constant peak ε(T) of (1−x)BT-xBMT ceramics become broad with increasing BMT content. During the temperature range of ε(T) peak summit, (1−x)BT-xBMT ceramics present quasi-linear dielectric phenomenon under high electric field with very high dielectric constant.     

Depression of the ferroelastic phase transition in LiCsSO<Subscript>4</Subscript> by uniaxial stress

In the lithium-caesium sulphate crystal in the temperature range of ferroelastic phase transition, the uniaxial stress σ _X induced changes in velocity and attenuation of the longitudinal ultrasonic wave propagating in the direction [010] are studied. The phase transition is close to the three-critical point and the critical exponent is κ = 0.27 ± 0.02. The stress applied drastically decreases the stepwise change in the wave velocity at T _C up to its disappearance at 2 MPa. In the temperature range between T _C and T _C − 6 K, the stress leads to an increase in the wave velocity and a decrease in its attenuation. This range was interpreted as that of co-existence of ferroelastic and incommensurate ordering, in which the stress influences the density of solitons leading to stiffening of the crystal lattice.     

Improvement of refrigerant capacity of La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> single crystal with a few percent Fe doping

Large low-field-induced magnetic entropy changes, ΔS _M, are observed in La_0.67Ca_0.33MnO₃ and La_0.67Ca_0.33Mn_0.96Fe_0.04O₃ single crystals. The peaks of ΔS _M broadened asymmetrically to high temperatures under higher magnetic fields for two materials should be attributed to the first-order magnetic phase transition at T _c. A small amount of iron doping results in an increase in the refrigerant capacity of the material though the magnetic entropy change decreases. The discovery of excellent magnetocaloric features of these single crystals in the low magnetic field can provide some ideas for exploring novel magnetic refrigerants operating under permanent magnet rather than superconducting one as magnetic field source. Supported by the State Key Project of Fundamental Research (Grant No. 2005CB724402), and the National Natural Science Foundation of China (Grant No. 50672126) Contributed by CHENG ZhaoHua     

Pressure-induced metamagnetic transition in the Cd<Subscript>0.7</Subscript>Mn<Subscript>0.3</Subscript>GeAs<Subscript>2</Subscript> ferromagnetic semiconductor

The magnetic susceptibility χ/χ₀ and the longitudinal Δρ _zz /ρ₀ and transverse Δρ _xx /ρ₀ magnetoresistances have been measured as functions of the hydrostatic pressure P ≤ 7 GPa at room temperature in the high-temperature ferromagnetic semiconductor Cd_0.7Mn_0.3GeAs₂ with a chalcopyrite structure and the Curie temperature T _c = 355 K. A pressure-induced metamagnetic transition from the low-magnetization state to the high-magnetization state has been observed in Cd_0.7Mn_0.3GeAs₂ near the magnetic ordering temperature. This transition is accompanied by the hysteresis of the magnetic susceptibility and magnetoresistance.     

Electronic structure of defective lithium cobaltites Li<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>CoO<Subscript>2</Subscript>

X-ray absorption, resonant X-ray emission, and X-ray photoelectron spectroscopical methods have been applied for the study of the electronic structure of defective lithium cobaltites Li _x CoO₂ (0.6≤x≤1.0). Resonant O K α X-ray emission spectra of LiCoO₂ showed localized excitonic states due to a dd transition between occupied and unoccupied Co 3d states. On the base of measurements of Co 3s X-ray photoelectron, Co 2p, and O 1s X-ray absorption spectra, it was established that in defective cobaltites the electronic holes are localized mainly in O 2p states. An evidence of phase separation in Li _x CoO₂ has been found. It was shown that the semiconductor-to-metal transition in Li _x CoO₂ (x<0.76) at about 160 K is not accompanied by changes in the Co 3d electronic configuration which remains 3d ⁶.     

Refractive indices of K<Subscript>2</Subscript>ZnCl<Subscript>4</Subscript> crystals in an incommensurate phase under uniaxial stresses

The influence of uniaxial mechanical stresses directed along the principal crystallophysical axes on refractiveindex temperature dependences in K₂ZnCl₄ crystals was studied. It is established that the refractive indices ni are quite sensitive to uniaxial stresses. Significant baric shifts of the paraphase–incommensurate–commensurate phase transition points to different temperature regions were observed, which is due to the effect of the uniaxial stress on the K₂ZnCl₄ crystal structure. It is found that applying uniaxial pressure increases the value of the temperature hysteresis of the commensurate–incommensurate phase transition.