Synthesis,growth and characterization of L-proline dimercuricchloride single crystals for frequency conversion applications

A semi-organic nonlinear optical L-proline dimercuricchloride (LPDMC) material has been synthesized. LPDMC single crystals were grown from aqueous solution by a slow cooling method. Good quality single crystals of size 19×6×3 mm³ have been grown over a period of 3 weeks. The grown crystals have been subjected to single crystal X-ray diffraction analysis to determine the cell parameters. The title compound crystallizes in the triclinic system with a noncentrosymmetric space group P1 and with unit-cell parameters a=7.2742(4) Å, b=9.4472(5) Å, c=10.4767(6) Å, α=108.621(3)^°, β=107.260(2)^°, γ=97.353(2)^° and volume=631.51(6) Å³. Optical and dielectric properties of the crystals have been studied. The thermal stability of the crystals was determined by thermogravimetric analysis/differential thermal analysis. The second harmonic generation efficiency of the crystals was obtained by the classical powder technique using a Nd:YAG laser and it is found to be 2.5 times that of potassium dihydrogen phosphate.     

A new crystalline HMX polymorph: ɛ-HMX

A new crystalline HMX polymorph, ?-HMX, was obtained. ?-HMX crystals were studied by X-ray structure analysis, optical microscopy, and differential scanning calorimetry. Their space group is P2₁/c. The unit cell parameters are a = 21.799(3) Å, b = 10.913(2) Å, c = 10.819(2) Å, and β = 97.43(2)°, V = 2552.15 ų, Z = 4. ?-HMX molecules are not equivalent in crystals and have chair conformations. The heat of the polymorphic transition of ?-HMX into the δ-polymorph was measured. The transition occurred with the intermediate formation of β-HMX. The dependence between the heats of polymorphic transitions and the densities of crystals of various HMX polymorphs was demonstrated. The character of this dependence was to a substantial extent determined by the type of HMX molecule conformation.     

Structural transformations of K<Subscript>3</Subscript>H(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystals with variations in temperature

Single crystals of the K₃H(SO₄)₂ compound are investigated using X-ray diffraction on Xcalibur S and Bruker diffractometers. The structure of the low-temperature monoclinic phase is refined (space group C2/c, z = 4, a = 14.698(1) Å, b = 5.683(1) Å, c = 9.783(1) Å, β = 103.01(1)°, T = 293 K, Bruker diffractometer), the structural phase transition is revealed, and the structure of the high-temperature trigonal phase is determined (space group R \(\bar 3\) m, z = 3, a = 5.73(1) Å,c = 21.51(1) Å,T = 458 K, Xcalibur diffractometer).     

Structure,microstructure, and thermopower of highest manganese silicide crystals grown from zinc solution-melt

MnSi_1.71–1.75 single crystals are grown using the combination of solidification from solution-melt and the Bridgman crystal growth technique. The single crystals represent tetrahedral bipyramids and correspond to the highest manganese silicide (HMS) modification with lattice parameters a = b = 5.52(1) Å and c = 65.7(8) Å. The thermopower measured between the parallel faces of these single crystals is anomalously high for plain HMS (180–190 μV/K).     

Structure and electrophysical properties of ferrocobaltites <Emphasis Type="Italic">Ln</Emphasis>BaFeCoO<Subscript>5 + δ</Subscript> (<Emphasis Type="Italic">Ln</Emphasis> = Tb,Dy, Ho,Y)

The ferrocobaltites LnBaFeCoO^{5 + δ} (Ln = Tb, Dy, Ho, Y) have been synthesized, and the parameters of their crystal structure have been determined. The thermal expansion, electrical resistivity ρ, and thermopower S of the synthesized compounds have been investigated in air at temperatures in the range from 300 to 1100 K. The compounds have a tetragonal structure (symmetry space group P4/mmm) with the unit cell parameters a = 3.9000 Å and c = 7.5922 Å (Ln = Tb, δ = 0.31), a = 3.8973 Å and c = 7.5679 Å (Ln = Dy, δ = 0.34), a = 3.8970 Å and c = 7.5507 Å (Ln = Ho, δ = 0.28), and a = 3.9029 Å and c = 7.5538 Å (Ln = Y, δ = 0.25). The ferrocobaltites under investigation are p-type semiconductors, and their electrical resistivity ρ and thermopower S decrease in the sequence Tb → Ho → Y → Dy (at room temperature). The linear thermal expansion coefficient of the LnBaFeCoO^{5 + δ} phases in the vicinity of the temperatures ranging from 465 to 535 K increases from (1.15?1.23) × 10^?5 to (1.73?1.93) × 10^?5 K^?1. The parameters of charge transfer in these ferrocobaltites have been determined. It has been found that an increase in the temperature leads to an increase in the excitation energy of charge carriers and a decrease in the activation energy of charge carrier transfer.     

Thin ferroelectric Nd-doped BiFeO<Subscript>3</Subscript> films with orthorhombic structure

X-ray diffraction and Raman spectroscopy of epitaxial Nd-doped bismuth ferrite films on MgO substrates reveal their orthorhombic symmetry Fmm2 (a = 7.914 Å, b = 7.913 Å, and c = 7.937 Å).     

Charge transfer over localized states in a TlS single crystal

It is revealed that TlS single crystals exhibit a variable range hopping conduction along a normal to their natural layers at temperatures T ≤ 230 K in a dc electric field and a nonactivated hopping conduction at low temperatures in strong electric fields. Estimates are made for the density of states near the Fermi level (N _F = 2.8 × 10²⁰ eV^?1 cm^?3 and their energy spread (ΔW = 0.02 eV), the localization radius (a = 33 Å), the average jump distance in the region of activated (R _av(T) = 40 Å) and nonactivated (R _av(F) = 78 Å) hopping conduction, and also the drop in the charge carrier potential energy along the jump distance in an electric field F: eFR = 0.006 and 0.009 eV at F = 7.50 × 10³ and 1.25 × 10⁴ V/cm, respectively.     

Synthesis,Crystal Structure and Luminescent Properties of Some Zn(II) Schiff Base Complexes: Experimental and Computational Study

A series of Zn(II)-Schiff bases I, II and III complexes were synthesized by reaction of o-phenylenediamine with 3-methylsalicylaldehyde, 4-methylsalicylaldehyde and 5-methylsalicylaldehyde. These complexes were characterized using FT-IR, UV-Vis, Diffuse reflectance UV-Vis, elemental analysis and conductivity. Complex III was characterized by XRD single crystal, which crystallizes in the triclinic system, space group P-1, with lattice parameters a?=?9.5444(2) Å, b?=?11.9407(2) Å, c?=?21.1732(3) Å, V?=?2390.24(7) ų, D _c ?=?1.408 Mg m^?3, Z?=?4, F(000)?=?1050, GOF?=?0.981, R1?=?0.0502, wR2?=?0.1205. Luminescence property of these complexes was investigated in DMF solution and in the solid state. Computational study of the electronic properties of complex III showed good agreement with the experimental data.     

M-Zentrenbildung in röntgenbestrahlten KCl-Kristallen

The production of F- and M-centres in KCl by X-irradiation has been studied at temperatures between ?20 °C and 50 °C. The optical absorption measurements could be conducted without interrupting the X-irradiation. The results can be summarized as follows: 1. In Harshaw KCl crystals the number of F-centres created by the so-called fast coloration process was proportional to the height of the absorption band at 204 mμ prior to the irradiation. 2. The F-centres formed by the fast process did not contribute to the formation of M-centres. 3. In crystals with a strong absorption band at 204 mμ unstable M-centres were observed, which decayed rapidly after the cessation of the X-irradiation. Their concentration was found to be independent of the F-centre concentration. 4. At temperatures below 0 °C the relation between the concentration of the stable M-centres and the F-centre concentration could not any longer be represented by [M]=k ₁₂·[F₁]·[F₂]+k ₂₂·[F₂]², F₁ and F₂ referring to the F-centres created respectively by the fast and the slow coloration process. Except at very low F₂-centre concentrations however the relationship [M]=k ₀+k ₂·[F₂]² represented the experimental data at all temperatures between ?20 °C and 50 °C. At constant temperaturek ₂ varied withL, the X-ray energy absorbed per unit time and unit volume, according to 1/k ₂=a+bL+cL ². The temperature dependence ofa ^?1 b ^?1 andc ^?1 could be approximated by Boltzmann factors. The corresponding activation energies wereE _a=0.12 eV,E _b=0.53 eV,E _c=0.97 eV.     

Crystal-Physical Model of Ion Transport in Nonlinear Optical Crystals of KTiOPO<Subscript>4</Subscript>

The ionic conductivity along the principal axes a, b, and c of the unit cell of the nonlinear-optical high-resistance KTiOPO₄ single crystals (rhombic syngony, space group Pna2₁), which are as-grown and after thermal annealing in vacuum, has been investigated by the method of impedance spectroscopy. The crystals were grown from a solution-melt by the Czochralski method. The as-grown KTiOPO₄ crystals possess a quasi-one-dimensional conductivity along the crystallographic c axis, which is caused by the migration of K⁺ cations: σ_║c = 1.0 × 10^–5 S/cm at 573 K. Wherein the characteristics of the anisotropy of ionic conductivity of the crystals is equal to σ_║c/σ_║a= 3 and σ_║c/σ_║b= 24. The thermal annealing at 1000 K for 10 h in vacuum increases the magnitude of σ_║c of KTiOPO₄ by a factor of 28 and leads to an increase in the ratio σ_║c/σ_║b= 2.1 × 10³ at 573 K. A crystal-physical model of ionic transport in KTiOPO₄ crystals has been proposed.     

Mössbauer study of the magnetocaloric compound AlFe<Subscript>2</Subscript><Emphasis Type="Bold">B</Emphasis><Subscript>2</Subscript>

Mössbauer spectroscopy in the ferromagnetic AlFe₂ B ₂ reveals T_c=299 K and shows good agreement with magnetic measurements. The crystals are plate-shaped. The flakes are found from X-ray diffraction to be in the crystallographic ac-plane in the orthorhombic system. The axes of the principle electric field gradient tensor are, by symmetry, colinear with the crystal a-, b- and c-axes. By using information about the quadrupole splitting and line asymmetry in the paramagnetic regime together with the quadrupole shift of the resonance lines in the ferromagnetic regime the magnetic hyperfine field direction is found to be in the ab-plane having an angle =40^° to the b-axis.     

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).     

Electrical conductivity and permittivity of the one-dimensional superionic conductor LiCuVO<Subscript>4</Subscript>

The electrical conductivity σ^a and permittivities ?^a, ?^b, and ?^c of a LiCuVO₄ single crystal have been measured along the a, b, and c crystallographic axes, respectively, in the temperature range 300–390 K at a frequency of 10³ Hz. The temperature dependences σ(T) and ?(T) were found to be typical for superionics.     

Probing the sign-changeable interaction between dark energy and dark matter with current observations

We consider the models of vacuum energy interacting with cold dark matter in this study, in which the coupling can change sigh during the cosmological evolution. We parameterize the running coupling b by the form b(a) = b_0 a + b_e(1-a), where at the earlytime the coupling is given by a constant b_e and today the coupling is described by another constant b_0. We explore six specific models with(i) Q = b(a)H_0ρ_0,(ii) Q = b(a)H_0ρ_(de),(iii) Q = b(a)H_0ρ_c,(iv) Q = b(a)Hρ_0,(v) Q = b(a)Hρ_(de), and(vi) Q = b(a)Hρ_c.The current observational data sets we use to constrain the models include the JLA compilation of type Ia supernova data, the Planck 2015 distance priors data of cosmic microwave background observation, the baryon acoustic oscillations measurements,and the Hubble constant direct measurement. We find that, for all the models, we have b_0 0 and b_e 0 at around the 1σ level,and b_0 and b_e are in extremely strong anti-correlation. Our results show that the coupling changes sign during the evolution at about the 1σ level, i.e., the energy transfer is from dark matter to dark energy when dark matter dominates the universe and the energy transfer is from dark energy to dark matter when dark energy dominates the universe.     

Quantifying Correlations via the Wigner-Yanase-Dyson Skew Information

In this paper, based on a discussion about the Wigner-Yanase-Dyson (WYD) skew information, the measure F_a,α(ρ_ab) for correlations in terms of the WYD skew information is introduced and discussed. The following conclusions are obtained. For a classical-quantum state ρ_ab, F_a,α(ρ_ab)=0 if and only if ρ_ab is a product state; F_a,α(ρ_ab) is locally unitary invariant and convex on the set of states with the fixed marginal ρ_a; F_a,α(ρ_ab) decreases under local random unitary operation on H_b; For a quantum-classical state ρ_ab, F_a,α(ρ_ab) decreases under local operation on H_b; Lastly, F_a,α(ρ_ab) is computed for the pure states and the Bell-diagonal states, respectively.     

Über Kristallstruktur und elektrische Eigenschaften der Wismutselenide Bi2Se2 und Bi2Se3

The properties of bismuth triselenide (Bi₂Se₃) are already known to a certain extent through the work of several authors, while it was still an open question whether there exists an individual solid phase of BiSe. Further information on this subject could be obtained by the successful growth and investigation of single crystals of both Bi₂Se₃ and Bi₂Se₂. X-ray analysis by means of goniometry, Weißenberg, Laue, and Debye-Scherrer diagrams confirmed the known crystal structure of Bi₂Se₃ (ditrigonal scalenohedral;D _3d ⁵ ?R—m; with the hexagonal axes:a=4·15 Å andc=28·55 Å, and 3 molecules per unit cell). As to Bi₂Se₂ it can be shown that it belongs to the same class but to a different space group (D _3d ¹ ?P— 1m orD _3d ³ ?P—m 1; hexagonal axes:a=4·15 Å,c=22·84 Å, unit cell: 3 molecules, if the formula Bi₂Se₂ is adopted). Common to both is a subcell with the dimensions:a′=a=4·15 Å andc′=5·71 Å. The temperature dependence of electrical conductivity and Hall coefficient was measured on several specimens having different crystal orientations. The most striking difference is the high anisotropy of Bi₂Se₃ (σ _a σ _c =10) as compared with Bi₂Se₂ (σ _a /σ _c <2). All specimens turned out to ben-type. The room temperature carrier concentration observed was:n (Bi₂Se3)=8·10¹⁸ cm^?3 andn (Bi₂Se₂)=4·10²⁰ cm^?3, the carrier mobility:μ(Bi₂Se3)=2·10³ cm²/V·s andμ(Bi₂Se₃)=20 cm²/V·s.     

Hyperfine Interactions in Pb<Superscript>3+</Superscript>F<Stack><Subscript>8</Subscript><Superscript>−</Superscript></Stack>F<Stack><Subscript>a</Subscript><Superscript>−</Superscript></Stack> clusters in fluorite crystals

The parameters of hyperfine interactions in Pb³⁺F ₈ ^? F _a ^? tetragonal clusters of MeF₂ crystals (Me=Ca, Sr, Ba) are interpreted. The contributions of the spin polarization to the parameters of the proper hyperfine interaction and additional (ligand) hyperfine interactions are calculated in the approximation of weak binding between a charge-compensating ion F _a ^? and a cubic fragment in the tetragonal cluster. It is demonstrated that correct inclusion of the contributions from the spin polarization to the ligand isotropic hyperfine interaction for the F _a ^? ion leads to anomalously large parameters of this interaction for MeF₂ crystals. These results are in agreement with experimental data.     

Crystal Structure,Luminescence and Triboluminescence of the Complex [Eu(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>3hmpa] NO<Subscript>3</Subscript>·HQuin

The atomic structure of crystals of the complex [Eu(NO₃)₂3hmpa] NO₃·HQuin , (hmpa – hexamethylphosphortriamide, HQuin – quinaldic acid) characterized by intensive luminescence and triboluminescence has been determined by the X-ray method. The noncentro-symmetric crystals of the compound are rhombic : a = 16.8193(3), b = 12.2877(2), c = 27.6516(5) Å, пр. гр. Pca2(1), Z = 4, ρ _{calc. .} = 1.427 g/сm³. The crystals have a structure of the insular type which is presented by the isolated complex molecules, outer-sphere NO₃ ^? – groups, and neutral molecules of quinaldic acid. Some structural aspects of formation of the luminescent and triboluminescent properties of the compound were discussed: the role of break planes in the crystal destruction was revealed.     

Synthesis,Crystal Structure,and Magnetic Properties of the YbFeTi<Subscript>2</Subscript>O<Subscript>7</Subscript> Compound

We report on the synthesis conductions and results of experimental investigations of the crystal structure and magnetic properties of a new magnetic compound YbFeTi₂O₇. According to the X-ray diffractometry data, the crystal structure of the investigated compound is described by the rhombic space group Pcnb with unit cell parameters of a = 9.8115(1) Å, b = 13.5106(2) Å, and c = 7.31302(9) Å and atomic disordering in the distribution of iron ions Fe³⁺ over five structural sites. The magnetic measurements in the lowtemperature region revealed a kink in the temperature dependence of the magnetic moment and its dependence on the sample magnetic prehistory. The experimental results obtained suggest that with a decrease in temperature the sample passes from the paramagnetic state to the spin-glass-like magnetic state characterized by a freezing temperature of T _f = 4.5 K at the preferred antiferromagnetic exchange coupling in the sample spin system. The chemical pressure variation upon replacement of rare-earth ion R by Yb in the RFeTi₂O₇ system does not change the crystal lattice symmetry and magnetic state.     

Specific features of anion transfer in HoF<Subscript>3</Subscript> crystals at high temperatures

The anionic conductivity of HoF₃ single crystals with a β-YF₃ structure (orthorhombic crystal system, space group Pnma) is investigated over a wide range of temperatures (323–1073 K). The unit cell parameters of HoF₃ crystals are as follows: a=0.6384±0.0009 nm, b=0.6844±0.0009 nm, and c=0.4356±0.0005 nm. It is revealed that the conductivity anisotropy of the HoF₃ crystals is insignificant over the entire temperature range covered. The crossover from one mechanism of ion transfer to another mechanism is observed near the critical temperature T_c≈620 K. The activation enthalpy of electrical conduction is found to be ΔH₁=0.744 eV at T<T_c and ΔH₂=0.43 eV at T>T_c. The fluorine vacancies are the most probable charge carriers in HoF₃ crystals. The fluorine ionic conductivities at temperatures of 323, 500, and 1073 K are equal to 5×10^?10, 5×10^?6, and 2×10^?3 S cm^?1, respectively.