Electronic and elastic properties of a double perovskite slab-rocksalt layer of Eu2SrAl2O7 investigated by LSDA+U

The electronic structure and elastic properties of a double perovskite slab-rocksalt layer compounds of Eu₂SrAl₂O₇ were calculated by local- (spin-) density approximation [L(S) DA] band theory with Hubbard term of U. We used and for the calculations. The band gap of Eu₂SrAl₂O₇ is 4.8 eV. Both of Eu-O and Al-O bonds have strong covalent character and Sr-O is a perfect ionic bond. The full set elastic constants indicate the elastic modulus of Eu₂SrAl₂O₇ is 224 and 240 GPa by calculation and experiment, respectively.     

High-temperature structural evolution of caesium and rubidium triiodoplumbates

CsPbI₃ and RbPbI₃ were investigated by in situ powder diffraction within temperature ranges of 298-687 K and 298-714 K, respectively. Both compounds crystallize in orthorhombic Pnma symmetry and expand isotropically upon a heating, revealing almost the same relative change of the lattice parameters. A pronounced difference in the structural evolution close to 600 K was observed, namely, CsPbI₃ undergoes first-order reversible phase transformation PnmaPnma+Pm3¯mPm3¯m, whereas no transitions (except of the sample's melting) in RbPbI₃ were detected. An attempt to clarify the relation between the existence/absence of a phase transition and bulging out of the iodine environment around alkaline ions was undertaken.     

Dilithium zirconium hexafluoride Li2ZrF6 at high pressures: A new monoclinic phase

Dilithium zirconium hexafluoride, Li₂ZrF₆ (, Z=1), is studied at high pressures using synchrotron angle-dispersive X-ray powder diffraction in a diamond anvil cell at room temperature. At atmospheric conditions, it has a structure with all the cations octahedrally coordinated to fluorine atoms. Above 10 GPa it transforms reversibly to a new polymorph (C2/c, Z=4), in which the coordination polyhedron of the Zr atoms is a distorted square antiprism, while the Li atoms are in the octahedral coordination. The LiF₆ octahedra form layers parallel to (100) that are connected by zig-zag chains of the edge-sharing Zr polyhedra running in the [001] direction. The relative change in volumes per one formula unit for both polymorphs is 6% at 11.8 GPa. The relations to other A₂BX₆-type structures are discussed.     

Prediction of lattice constant in cubic perovskites

Regularities of lattice constant in ideal perovskites are investigated by using a total of 132 ABX₃-type compounds, including oxides and halides. Two atomic properties; the sum of ionic radius of B and X atoms and the well known ‘tolerance factor’ (which is a function of ionic radius of A, B and X), were found very effective in reproducing the measured lattice constant through a linear combination of these two parameters (R²=0.995). It is further indicated that these two parameters are linked to the crystal features of perovskite. The average error limits in predicting lattice constant, by using this empirical equation, are expected within 0.63%. It may be useful to design new substrates/buffer materials for compound semiconductor epitaxy, in which there is a requirement of lattice match between them and adjacent layers.     

Pressure dependence of electronic structure and magnetic properties in Fe16N2

The electronic structures and magnetic properties of Fe₁₆N₂ system and their pressure dependence were investigated by using first-principles calculations based on the density functional theory. It has been found that the total magnetic moment in Fe₁₆N₂ system decreases monotonically as increasing pressure from 0 to 14.6 GPa. A phase transition from ferromagnetic (FM) to non-magnetic (NM) occurs with a volume collapse of around 0.008  at 14.6 GPa, The lattice constants a and c for magnetic results decrease monotonically as pressure increasing from 0 to 14.6 GPa, at 14.6 GPa, the lattice constant a decreases sharply, on the contrary, the lattice constant c increases abruptly. We think that the change of microscopic structure of Fe₁₆N₂ is responsible for the phase transition from FM to NM.     

Quantum critical behaviour in doped Y bB12 studied by ab initio calculations

The Kondo insulator Y bB₁₂ is known to undergo a transition to the metallic state with doping or under an external magnetic field. Within the virtual crystal approximation (VCA), we calculated the occupation of the Yb 4f and 5d shells, and , as a function of doping of Y bB₁₂ with the rare earths Tm and Lu. We found that exhibits an anomalous change at the critical concentration of the dopant, in agreement with experiment ( for Y b_1−xLu_xB₁₂ and for Y b_1−xTm_xB₁₂). We suggest that the critical behaviour seems to be strictly connected with the change of and in consequence the change of the Yb valency.     

Physicochemical, structural and fluorescence properties of Er-doped Ge-S-Ga glasses

Erbium-doped (GeS₂)_x(Ga₂S₃)_100−x (x=75, 80, 85, 90 mol%) glasses have been characterized by some basic parameters, which are important from a practical point of view. The influence of Er by introduction of 0.3, 0.6, and 0.9 mol% Er₂S₃ on the properties has been studied. The glasses have relatively high glass transition temperatures and high thermal stability, the maximal being at x=80 (the difference between the crystallization and glass transition temperatures has been found to be 150 °C. The values of Vickers microhardness and density increase with increasing GeS₂ content, slightly depending on the presence of the Er³⁺ ions. The distribution and changes of the structural units, caused by addition of Ga₂S₃ and Er₂S₃ to GeS₂, have been specified by the Raman scattering in the range 50-550 cm⁻¹. The intensity dependence of the luminescence on glass composition has been evaluated. The glasses have shown a good chemical durability and their resistance to the moisture is relatively high. The obtained results have supported possible applications of these glasses in rare-earth doped devices.     

The effect of the Bi source on optical properties of Bi2Te3 nanostructures

nanostructures were synthesized by using different Bi sources via a simple solvothermal process, in which and BiCl₃ were used as the Bi sources. Optical properties of nanostructures prepared with and BiCl₃ as the Bi sources were investigated by micro-Raman spectroscopy. The Raman scattering spectrum of hexagonal nanoplates prepared by using as the Bi source shows that the infrared (IR) active mode A_1u, which must be odd parity and is Raman forbidden for bulk crystal due to its inversion symmetry, is greatly activated and shows up clearly in the Raman scattering spectrum. We attribute the appearance of the infrared active A_1u mode in the Raman spectrum to crystal symmetry breaking of hexagonal nanoplates. However, the Raman scattering spectrum of nanostructures with irregular shape prepared by using as the Bi source only exhibits the two characteristic Raman modes of crystals. Micro-Raman measurements on nanostructures with different morphologies offer us a potential way to tailor optical properties of nanostructures by controlling the morphologies of the nanostructures, which is very important for practical applications of nanostructures in thermoelectric devices.     

Structure instability of A2Al2B2O7 (A=K, Na) crystals

A theoretical study on the stabilities of the crystal structures of K₂Al₂B₂O₇ (KABO) and Na₂Al₂B₂O₇ (NABO) has been carried out using density functional theory with generalized-gradient corrections. All structures have been optimized by minimizing the total energies with respect to lattice constants and to the atomic coordinates within the unit cell. In the case of KABO, the structure with space group P321 always takes energy advantage over the whole volume range studied, whereas on both volume expansion and contraction, the original NABO structure becomes unstable, taking a structure transition from its space group to the P321 space group of KABO structure. The theoretical predictions were well realized in the experimental results on the structure changes of the (K_1−xNa_x)₂Al₂B₂O₇ solid solution system.     

Thermal expansion and magnetostriction of GdAg2, and relations to the magnetoelastic paradox

The antiferromagnet GdAg₂ has been shown to be a good model system for the magnetoelastic paradox (MEP), because it exhibits large symmetry conserving magnetoelastic strains and the antiferromagnetic propagation vector breaks the tetragonal lattice symmetry (therefore a large symmetry breaking magnetoelastic strain can be expected in a single magnetic structure). As in many similar Gd based compounds no symmetry breaking strain has been found in the experiment. In order to investigate this MEP further, we have measured magnetostriction and magnetization on a textured polycrystal. The behaviour closely resembles that of GdNi₂B₂C, the prototype system for the magnetoelastic paradox (MEP). Our forced magnetostriction data indicate that the crystal distorts in applied magnetic field and gives further evidence that the MEP is a low field effect. The observed phase transitions are in agreement with available specific heat and neutron diffraction data. Moreover, the saturation magnetic field was measured in high pulsed magnetic fields and agrees well with the value calculated from the Standard Model of Rare Earth Magnetism (SMREM).     

Physical properties of BaMg1/3Nb2/3O3-BaCo1/3Nb2/3O3 solid solutions

Structural, electric and magnetic properties of Ba₃Mg_1−xCo_xNb₂O₉ based dielectric ceramic compounds have been studied. The samples, prepared by a solid state reaction method, were characterised by X-ray powder diffraction (XRPD), electron microscopy (SEM), dielectric (ε(T)) and magnetic measurements (χ⁻¹(T)). The XRPD analyses showed that the crystal structure of these compounds does change by the increase of substitution degree, passing from a superstructure hexagonal-type, (no. 164), space group (SG) to a simple structure cubic-type, (no. 221), SG. However, the evolution of the elementary unit cell lattice parameter can be followed and it exhibit a linear increasing tendency with increase in the substitution, indicating the existence of a solid solution through out the investigated range of substitution (0-1). The microstructure analysis shows a variation in the grain size and also the porosity of the samples with the degree of substitution. The results are in good agreement with that of dielectric measurements, which also showed that the dielectric constant (ε) increases with the increase of cobalt content. The magnetic characterization of cobalt substituted samples showed an antiferromagnetic type super-exchange interaction between these magnetic ions. At the same time, the values of effective magnetic momentum (μ_eff) are close to the value that corresponds to Co²⁺ free ions. The study highlights the possibility of modelling these materials by substitutions, in order to improve properties of negative-positive-zero (NPO) type dielectric applications.     

Optical phonon modes and structure of ZnGa2Se4 and ZnGa2S4

We present the infrared and Raman study of the optical phonon modes of the defective compounds ZnGa₂Se₄ and ZnGa₂S₄. Most of the compounds have been found to crystallize in the thiogallate structure (defect chalcopyrite) with space group where all cations and vacancies are ordered. For some Zinc compounds a partially disordered cationic sublattice with various degrees of cation and vacancy statistical distribution, which lead to the higher symmetry (defect stannite), has been reported. For ZnGa₂Se₄ we have found three modes of A symmetry, showing Raman activity only. In addition, we have observed each five modes of B and E symmetry, showing infrared as well as Raman activity. The number of modes and their symmetry assignment, based on polarized measurements, clearly indicate space group for the investigated crystals of ZnGa₂Se₄.Regarding ZnGa₂S₄ we have found three modes exclusively showing Raman activity (2A⊕1B₁), and only eight modes showing infrared as well as Raman activity (3B₂⊕5E). The assignment of the modes has been derived by analyzing the spectral positions of the vibrational modes in comparison to a number of compounds. From the number and symmetry assignment of the optical phonon modes we confirm that ZnGa₂S₄ most likely crystallizes in space group .     

Electron-ion recombination and photoionization of Fe XXI

Results for electron-ion recombination and photoionization of , with emphasis in high-temperature region, are presented from ab initio unified method. The unified method, based on close coupling (CC) approximation and R-matrix method, (i) subsumes both the radiative recombination (RR) and dielectronic recombination (DR), (ii) enables self-consistent sets of photoionization and recombination cross sections from using an identical wavefunction for both the processes, and (iii) provides state-specific recombination rates of a large number of bound states. A large CC wavefunction expansion, which includes the ground and 28 core excitations of n=2 and 3 complexes and span a wide energy range, has been used. Compared to Δn=2-2, Δn=2-3 core excitations are found to introduce strong resonant structures and enhance the background photoionization cross sections (σ_PI) in the high-energy region. These features along with prominent photoexcitation-of-core (PEC) resonances at n=3 core thresholds have increased the unified total recombination rate coefficients (α_R(T)) at temperatures , region of maximum abundance of the ion in collisional equilibrium, by a factor of 1.6 over previous calculations. State-specific recombination rate coefficients α_R(nLS), which include both the RR and DR, are presented for the first time for 685 bound states with n?10 and l?9. The unified total recombination rate with photoelectron energy α_R(E) is presented and the role of low-energy near-threshold fine structure resonances is illustrated. The present results should provide a reasonably complete self-consistent set of recombination rates and photoionization cross sections for astrophysical modelings of high-temperature plasmas from optical to far-ultraviolet wavelength regions.     

Giant optical anisotropy in R-plane GaN/AlGaN quantum wells caused by valence band mixing effect

This study investigates the optical anisotropy spectrum in the R-plane (i.e., the -oriented layer plane) of GaN/Al_0.2Ga_0.8N quantum wells of different widths. The optical matrix elements in the wurtzite quantum wells are calculated using the k⋅p finite difference scheme. The calculations show that the valence band mixing effect produces giant in-plane optical anisotropy in -oriented GaN/Al_0.2Ga_0.8N quantum wells with a narrow width. The nature of the in-plane optical anisotropy is found to be dependent on the well width. Specifically, it is found that the anisotropy changes from x^′-polarization to y^′-polarization as the well width increases.     

Anisotropic spin fluctuations in CeCoIn5

CeCoIn₅ is an unconventional heavy fermion superconductor with a relatively large transition temperature . NMR measurements of the spin lattice relaxation rate at the In(1) site reveal a significant anisotropy of the fluctuating hyperfine fields, which reverses below 30 K. These results suggest that two-dimensional fluctuations of the Ce 4f moments are relevant for the superconducting pairing.     

Low-field magnetic properties of LaMnO3+δ with 0.065≤δ≤0.154

In a weak magnetic field LaMnO_3+δ exhibits at δ=0.065 below the paramagnetic-to-ferromagnetic (FM) Curie temperature, T_C, a mixed (spin-glass and FM) phase followed by a frustrated FM phase at δ between 0.100 and 0.154. The same behavior is observed in La_1−xCa_xMnO₃ with x between 0 and 0.3. This can be understood by the similar variation of the Mn⁴⁺ concentration, c between ≈0.13 and 0.34, in both materials when x or δ is increased. On the other hand, considerable differences are found between these compounds in the values of the magnetic irreversibility, in the dependencies of T_C(c) and the magnetic susceptibility, χ(c), as well as in the critical behavior of χ(T) near T_C. These differences can be explained by distortions of the cubic perovskite structure, by the reduced lattice disorder and by the more homogeneous hole distribution in LaMnO_3+δ than in La_1−xCa_xMnO₃.     

Ab initio electronic band structure calculation of InP in the wurtzite phase

We present ab initio calculations of the InP band structure in the wurtzite phase and compare it with that of the zincblende phase. In both calculations, we use the full potential linearized augmented plane wave method as implemented in the WIEN2k code and the modified Becke-Johnson exchange potential, which provides an improved value of the bandgap. The structural optimization of the wurtizte InP gives , , and an internal parameter u=0.371, showing the existence of a spontaneous polarization along the growth axis. As compared to the ideal wurtzite structure (that with the lattice parameter derived from the zincblende structure calculations), the actual wurtzite structure is compressed (−1.3%) in plane and expanded (0.7%) along the c-direction. The value of the calculated band gaps agrees well with recent optical experiments. The calculations are also consistent with the optical transitions found using polarized light.