Organic superalkalis with closed-shell structure and aromaticity

Benzene (C₆H₆) and polycyclic hydrocarbons such as naphthalene (C₁₀H₈), anthracene (C₁₄H₁₀) and coronene (C₂₄H₁₂) are well known aromatic organic compounds. We study the substitution of Li replacing all H-atoms in these hydrocarbons using density functional method. The vertical ionisation energy of such lithiated species, i.e. C₆Li₆, C₁₀Li₈, C₁₄Li₁₀ and C₂₄Li₁₂ ranges 4.24–4.50 eV, which is lower than the ionisation energy (IE) of Li atom. Thus, these species may behave as superalkalis due to their lower IE than alkali metal. However, these lithiated species possess planar and closed-shell structure, unlike typical superalkalis. Furthermore, all Li-substituted species are aromatic although their degree of aromaticity is reduced as compared to corresponding hydrocarbon analogues. We have further explored the structure of C₆Li₆ as star-like, unlike its inorganic analogue B₃N₃Li₆, which appears as fan-like structure. We have also demonstrated that the interaction of C₆Li₆ with a superhalogen (such as BF₄) is similar to that of a typical superalkali (such as OLi₃). This may further suggest that the proposed lithiated species may form a new class of closed-shell organic superalkalis with aromaticity.     

Determination of isotropic and anisotropic knight shift in V3X compounds

Methods are described to determine the isotropic as well as the anisotropic part of the Knight shift from powdered samples of several V₃X compounds (V₃Co, V_77.5Ni_22.5, V₃Rh, V₃Pd, V₃Pt and V₃Ir). Measurements of the Knight shifts of the central line as well as the satellites prove to be necessary. The obtained values for K_iso are about 0.5% while K_ax is not larger than 0.03%.The influence of the X elements on the quadrupolar interaction frequency v_Q will be discussed.     

Comparative study of structural and magnetic properties of NiZnCu ferrite powders prepared via chemical coprecipitation method with different coprecipitators

We prepared NiZnCu ferrite powders with nominal composition Ni_0.4−xZn_0.6Cu_xFe₂O₄ (x=0-0.2) via chemical coprecipitation method with NaOH and Na₂CO₃ as coprecipitators. The structural and magnetic properties of these compounds were studied and compared. It is found that all the specimens exhibit single-phase structure after annealing. The saturation magnetization of specimens with NaOH as coprecipitator is lower than that with Na₂CO₃ as coprecipitator. It is also found that the growth of grains is hindered for specimens using Na₂CO₃ as coprecipitator.     

Vibrational relaxation in CD4 and CD4-rare gas mixtures

Using the optic-acoustic effect, measurements of the relaxation time were made after exciting the v₄ mode of CD₄. This was done for pure CD₄ and for mixtures of CD₄ with He, Ne, Ar and Kr, the results being 3.9±0.2, 1.8±0.2, 18±2, 70±15 and ? 100 μs at 1 atm, respectively. From the relaxation time dependence on mass as well as from a comparison between results for CH₄ and CD₄ it is concluded that energy transfer takes place via a vibration-rotation-translation (V-R-T) mechanism.Experiments were also conducted to study the most probable deexcitation path from the higher energy mode, v₃, to translation. This was done for CD₄-CD₄ as well as for CD₄-atom collisions. For pure CD₄ deexcitation occurs via the lower energy group (v₂, v₄), while for CD₄ mixtures it may also occur via the higher energy group (v₁, 2v₂, v₂ + v₄, 2v₄).     

The universality of the electron spin relaxation in C60 mono radical anion salts: EPR studies of the model system [P(C6H5)4]2C60X

The C₆₀ radical anion salts [P(C₆H₅)₄]₂C₆₀X (X=Cl, Br, I) are grown via electrocrystallization and used as a model system to study the electron spin and nuclear spin dynamics as well as the molecular dynamics of C₆₀ mono anions in the solid state, which obey universal laws. It is shown that [P(C₆H₅)₄]₂C₆₀X is an exception among the fullerides, since the temperature dependence of the JT distortion, predicted for ionic C₆₀, can be deduced.     

Effect of TiO2 addition on the crystallization of quenched glasses in the SiO2–Al2O3–ZrO2 system

The glass formation in the SiO₂-rich region of the ternary oxide system Al₂O₃–ZrO₂–SiO₂ with MgO, CaO, and TiO₂ as melting aids was analyzed. The crystallization of glasses with different content of TiO₂ and phase evolution with the temperature was studied by X-ray diffraction, infrared, laser Raman spectroscopy and transmission electron microscopy. The use of TiO₂ favored formation and crystallization of the glasses due to the decrease of the viscosity of melts and acting as a nucleating agent. The crystalline phase of t-ZrO₂ was developed at temperatures as low as 880°C whereas in as prepared specimens without TiO₂ its presence was not detected. For the specimens with TiO₂, t-ZrO₂ and mullite were the principal phases at 1000°C. TiO₂ addition did not change the crystallization sequence but decreased the formation temperature of the crystalline phases. Most of Ti⁴⁺ ions entered into t-ZrO₂ and only a small portion in mullite, but the surplus was detected in ZrTiO₄.     

Preparation of proton conducting BaCe0.8Gd0.2O3 thin films

Thin films of BaCe_0.8Gd_0.2O₃ were prepared by solid state reaction of two screen-printed layers over porous substrates. The first layer consists of the oxygen ion conductor Ce_0.8Gd_0.2O₂ with a fluorite structure, whereas the top layer consists of BaCO₃. After decomposition of the carbonate, BaO reacts with Ce_0.8Gd_0.2O₂ forming the perovskite oxide BaCe_0.8Gd_0.2O_3−δ with protonic conductivity. The in-situ reaction and densification on the porous substrates results in gastight thin layers of 10 to 50 μm and allows overcoming the problems due to the poor sinterability of the proton conductor. Two different porous substrates prepared by warm-pressing were studied as membrane supports, i.e., (i) porous composite NiO–Zr_0.85Y_0.15O₂, commonly employed as solid oxide fuel cell anode and (ii) porous Ce_0.8Gd_0.2O₂ oxide. The structural properties of the layer, compositional gradients and occurring phases are described, as well as water uptake, gastightness (He leaking rate) and emf measurement. Protonic conducting membranes are particularly suited not only for hydrogen separation combined with reforming and water–gas-shift converters but also as a protonic fuel cell electrolyte.     

Glass formation in the As2Se3-As2Te3-Sb2Te3 system

Chalcogenide glasses from the As₂Se₃-As₂Te₃-Sb₂Te₃ system were synthesized for the first time. The glass-forming region was determined by X-ray diffraction and electron microscopic analyses.The basic physicochemical parameters such as density (d), microhardness (HV) and temperatures of phase transformations (glass transition T_g, crystallization T_cr and melting T_m) were measured. Compactness and some thermomechanical characteristics such as volume (V_h) and formation energy (E_h) of micro-voids in the glassy network as well as the elasticity module (E) were calculated. The glass-forming ability was evaluated according to Hruby's criteria (K_G). The correlation between composition and properties of the (As₂Se₃)_x(As₂Te₃)_y(Sb₂Te₃)_z glasses was established and comprehensively discussed.     

K0.5Bi0.5TiO3—Na0.5Bi0.5TiO3系统铁电陶瓷相界的X射线研究

用X射线衍射方法测定了K_0.5Bi_0.5TiO₃—Na_0.5Bi_0.5TiO₃系统不同组分试样的点阵常数和相变温度,确定了四方-三方相界组成。给出了K_0.5Bi_0.5TiO₃和Na_0.5Bi_0.5TiO₃的多晶X射线衍射数据。 关键词：     

Spin-dependent current and magnetization reversal in Tb22Co5Fe73/Pr6O11/Tb19Co5Fe76 nanofilms in laser radiation field

The results of investigation of magnetization reversal dynamics of ferrimagnetic amorphous nanolayers with transverse anisotropy is investigated for Al₂O₃/Tb₂₂Co₅Fe₇₃/Al₂O₃ and Al₂O₃/Tb₂₂Co₅Fe₇₃/Pr₆O₁₁/Tb₁₉Co₅Fe₇₆/Al₂O₃ multilayer films irradiated by laser pulses, as well as the effect of such irradiation on the resistance in a Tb₂₂Co₅Fe₇₃/Pr₆O₁₁/Tb₁₉Co₅Fe₇₆ tunnel microcontact. It is shown that magnetization reversal in magnetic nanolayers in the laser radiation field may occur not only because of heating and the action of the external magnetic field, but also under the action of the magnetic field induced by circularly polarized laser radiation, as well as owing to transfer of magnetic moments by polarized electrons. Laser radiation can be used to control (by changing the resistance by a factor of 1.5–2.0) the conductivity of the Tb₂₂Co₅Fe₇₃/Pr₆O₁₁/Tb₁₉Co₅Fe₇₆ tunnel microresistor. Original Russian Text ? N.N. Krupa, 2009, published in Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2009, Vol. 108, No. 5, pp. 981–992.     

Propagation of spectral Stokes singularities of stochastic electromagnetic beams through atmospheric turbulence

The propagation of spectral Stokes singularities (vortices) of stochastic electromagnetic vortex beams through atmospheric turbulence is studied, where the electromagnetic Gaussian Schell-model (GSM) vortex beam is taken as an illustrative example. It is shown that the spectral Stokes vortices S ₁₂ (C-points), S ₂₃ and S ₃₁ introduced to describe the polarization singularities of stochastic electromagnetic beams appear in turbulence. The motion, creation, annihilation and polarization changes of S ₁₂, S ₂₃ and S ₃₁ vortices, as well as the handedness inversion of S ₁₂ vortices may appear as the propagation distance or one beam parameter varies. In the process the topological relationship holds true. In comparison with the free-space propagation, the variation of the refractive index structure constant C_n²C_{n}^{2} in atmospheric turbulence results in similar effects as above. The dependence of S ₁₂, S ₂₃ and S ₃₁ vortices on the propagation distance and beam and turbulence parameters are illustrated by numerical examples.     

On the metal distribution in the system GeTe−Sb2Te3

The structures of GeSb₂Te₄, Ge₂Sb₂Te₅ and GeSb₄Te₇ are not determined completely by means of classical X-ray or electron diffraction studies. We have measured the Mössbauer parameters of¹²¹Sb in these compounds as well as in their binary constituent Sb₂Te₃ as an attempt to improve our knowledge on the question.     

Compatibility study of oxide and olivine cathode materials with lithium aluminum titanium phosphate

The compatibility of the solid electrolyte Li_1.5Al_0.5Ti_1.5(PO₄)₃ (LATP) with the cathode materials LiCoO₂, LiMn₂O₄, LiCoPO₄, LiFePO₄, and LiMn_0.5Fe_0.5PO₄ was investigated in a co-sintering study. Mixtures of LATP and the different cathode materials were sintered at various temperatures and subsequently analyzed by thermal analysis, X-ray diffraction, and electron microscopy. Oxide cathode materials display a rapid decomposition reaction with the electrolyte material even at temperatures as low as 500 °C, while olivine cathode materials are much more stable. The oxide cathode materials tend to decompose to lithium-free compounds, leaving lithium to form Li₃PO₄ and other metal phosphates. In contrast, the olivine cathode materials decompose to mixed phosphates, which can, in part, still be electrochemically active. Among the olivine cathode materials, LiFePO₄ demonstrated the most promising results. No secondary phases were detected by X-ray diffraction after sintering a LATP/LiFePO₄ mixture at temperatures as high as 700 °C. Electron microscopy revealed a small secondary phase probably consisting of Li₂FeTi(PO₄)₃, which is ionically conductive and should be electrochemically active as well.     

Studies on self-pumped phase conjugation in Cu-doped (K0.5Na0.5)0.2(Sr0.61Ba0.39)0.9Nb2O6 crystals

The use of Cu-doped (K_0.5Na_0.5)_0.2(Sr_0.61Ba_0.39)_0.9Nb₂O₆ as self-pumped phase conjugators using internal reflection is reported. Reflectivities as high as 63% at 5145.5 nm and 60% at 632.8 nm were realized. It was found that the photorefractive response changes significantly at different doping concentration. The responses of the crystals to the laser wavelength, incident angle and dopant concentration are studied.     

Laser Induced Energy Transfer Studies in Polyatomic Mixtures: CH3F-NO2

Abstract

The internal kinetics of NO₂ as well as the kinetics of crossover between CH₃F and NO₃ were studied in mixtures of these polyatomics and rare gases.

Subsequent to excitation of the CH₃F to v ₃=1 by the P(20) line of a 9.6μ Q-switch CO₂ laser, fluorescence of NO₂ at 6.12μ from v ₃=1 was monitored.

The equilibration rate of the stretching modes in NO₂ was determined to be 46 ± 10 msec^?1 torr^?1 while the rate of stretches-bend equilibration was measured as 15 ± 3 msec^?1 torr^?1. The rate of crossover from excited CH₃F to NO₂ in high rare gas dilution was measured as 90 ± 20 msec^?1 torr^?1 and the reverse rate as 285 ± 60 msec^?1 torr^?1.

Comparison to other triatomic systems as well as other experiments with mixtures of polyatomics are made and implications of laser “photochemistry” of NO₂ reactions are discussed.     

The investigations of phases with general formula M2FeV3O11, where M=Mg,Co, Ni,Zn by IR and Mössbauer spectroscopy

Phases of general formula M₂FeV₃O₁₁, where M=Mg, Co, Ni and Zn as well as the orthorhombic modification of FeNb₁₁O₂₉, have been investigated by the help of IR and Mössbauer spectroscopy. It was found that the isostructural compounds Co₂FeV₃O₁₁, Mg₂FeV₃O₁₁, Zn₂FeV₃O₁₁, as well as Ni₂FeV₃O₁₁ with a different structure have one single and almost identical chemical environment for iron(III). The large Mössbauer quadrupole splitting measured suggests that iron(III) is located in a highly distorted octahedron. The IR spectra of three isostructural M₂FeV₃O₁₁ compounds are similar but differ from that of Ni₂FeV₃O₁₁. The Mössbauer spectrum of orthorhombic FeNb₁₁O₂₉ has been fitted with two doublets, their hyperfine parameters indicating iron in distorted octahedral environment.     

The ν9 + ν11 − ν11, ν10 + ν11 − ν11 hot band system in allene-d4

The hot band system ν₉ + ν₁₁ ? ν₁₁, ν₁₀ + ν₁₁ ? ν₁₁ in allene-d₄ was studied at a resolution near 0.010 cm^?1. About 1500 partly overlapped hot band rotational lines were assigned and fitted to a model taking into account z-Coriolis resonance between the combination levels ν₉ + ν₁₁ and ν₁₀ + ν₁₁ as well as vibrational l-type resonances within these levels. Upperstate constants have been derived from an analysis in which the constants for the ν₁₁ level were constrained. A detailed study of rotational as well as vibrational l-type doublings occurring in the KΔK = ?1 subband is presented, and the sign of vibrational l-type doubling constants for the ν₁₀ + ν₁₁ level is determined. A localized (x, y)-Coriolis resonance between ν₁₀ + ν₁₁ and ν₄(B₁) + ν₁₁ is discussed and the interaction parameter is obtained as well as some constants for ν₄ + ν₁₁.     

Temperature dependence of magnetostriction in [Co1−x(FeNi)x]75Si15B10 amorphous alloys

Magnetostriction measurements as a function of temperature and composition are reported for [Co_1x(Fe_0.5Ni_0.5)_x]₇₅Si₁₅B₁₀ metallic glasses. Single-ion as well as two-ion contributions to λ_s are found in the composition range 0<x<0.5. For x=0.12 the magnetostriction changes sign with increasing temperature.     

Spectroscopic studies of the high-Tc superconducting cuprate perovskites

We present XRD, ESR, IR, DR(UV, VIS) as well as resistivity and magnetic susceptibility data of single phase superconducting perovskites YBa₂Cu₃O_x and EuBa₂Cu₃O_x. A rich phonon structure for both oxide compounds has been observed with a peak at: 72, 108, 135, 148, 172, 570 and 620 cm^-1. The edge of the low energy side was observed at 55 cm^-1. The estimated carrier density for YBa₂Cu₃O_x is (1–2) × 10²¹ cm^-3. A weak ESR signal has also been observed for superconducting phases which is associated with the lattice defects.We also report ESR and optical measurements of constitutent materials as well as not superconducting phases Y₂Cu₂O₅ and BaCuO₂.     

The fabrication of ReS2 flowers at controlled locations by chemical vapor deposition

Here we report a metal induced nucleation to realize the growth of ReS₂ flowers at controlled locations. The ordered arrays of ReS₂ flowers have been successfully prepared on SiO₂/Si substrate using Pt metal dots as nucleation sites and S, NH₄ReO₄ powders as precursors by a chemical vapor depostion method. The NH₄ReO₄ powders are used as the rhenium sources. The ReS₂ flowers are grown above the pre-patterned Pt dots, Raman and transmission electron microscopy measurements indicated that the prepared ReS₂ flowers have excellent crystalline quality.