Dielectric relaxation in polar nematic liquid crystals

The relationship between the complex dielectric permittivity tensor of a polar nematic liquid crystal and the autocorrelation matrix for the permanent dipole moment of a molecule is obtained. The theory is applicable to the whole frequency range which characterizes orientational relaxation in liquid crystals (up to ∼ 5 THz). The models of rotational diffusion and extended rotational diffusion in a mean field nematic potential are used to evaluate the dielectric absorption and dispersion in nematics.     

Easy α- to β-migration of an enol moiety on a pyrrole ring

Functionalized pyrrolic enols, 2-(2,2-dicyano-1-hydroxyethenyl)-1-methylpyrroles, synthesized from 2-ethenylpyrroles by a nucleophilic SEt-OH exchange, upon heating (75-142 °C) are readily rearranged to their 3-isomers in near to quantitative yield. The inter or intramolecular auto-protonation of a pyrrole ring by the acidic enol hydroxyl to form a mesomeric pyrrolium cation or zwitterion is suggested to be a key step in the rearrangement.     

Long-range chemical interactions in solid-state reactions: effect of an inert Ag interlayer on the formation of L10-FePd in epitaxial Pd(0 0 1)/Ag(0 0 1)/Fe(0 0 1) and Fe(0 0 1)/Ag(0 0 1)/Pd(0 0 1) trilayers

The effect of 0, 0.5, and 1?μm-thick Ag interlayers on the chemical interaction between Pd and Fe in epitaxial Pd(0?0?1)/Ag(0?0?1)/Fe(0?0?1)/MgO(0?0?1) and Fe(0?0?1)/Ag(0?0?1)/Pd(0?0?1)/MgO(0?0?1) trilayers has been studied using X-ray diffraction, ⁵⁷Fe Mössbauer spectroscopy, X-ray photoelectron spectroscopy, and magnetic structural measurements. No mixing of Pd and Fe occurs via the chemically inert Ag layer at annealing temperatures up to 400?°C. As the annealing temperature is increased above 400?°C, a solid-state synthesis of an ordered L1₀-FePd phase begins in the Pd(0?0?1)/Ag(0?0?1)/Fe(0?0?1) and Fe(0?0?1)/Ag(0?0?1)/Pd(0?0?1) film trilayers regardless of the thickness of the buffer Ag layer. In all samples, annealing above 500?°C leads to the formation of a disordered Fe_xPd_1?x(0?0?1) phase; however, in samples lacking the Ag layer, the synthesis of Fe_xPd_1?x is preceded by the formation of an ordered L1₂-FePd₃ phase. An analysis of the X-ray photoelectron spectroscopy results shows that Pd is the dominant moving species in the reaction between Pd and Fe. According to the preliminary results, the 2.2?μm-thick Ag film does not prevent the synthesis of the L1₀-FePd phase and only slightly increases the phase’s initiation temperature. Data showing the ultra-fast transport of Pd atoms via thick inert Ag layers are interpreted as direct evidence of the long-range character of the chemical interaction between Pd and Fe. Thus, in the reaction state, Pd and Fe interact chemically even though the distance between them is about 10⁴ times greater than an ordinary chemical bond length.     

Synthesis,spatial structure and spectral properties of pyrylo‐4 (thio) squaraines variously substituted in cyclobutene moiety

Synthetic routes have been developed to a number of (thio) squaraine dyes containing the residues of CH‐acids at the central cyclobutene ring. The electronic and spatial structure as well as the chemical conversions and optical behaviour of the compounds obtained have been studied both theoretically and by X‐ray diffraction analysis, ¹H NMR and electronic spectroscopy. As shown, the electronic nature and sterical characteristics of the central ring substituents give rise to some general conformational features and crystal packing regularities and also govern the spectral position of the first π–π^* absorption band. The structure–property relationships established in the study provide guidance for the purposeful design of deeply coloured (thio) squaraines. Copyright © 2015 John Wiley & Sons, Ltd.     

Transannular additions of selectfluor and xenon difluoride: regioselectivity and mechanism

The addition of 1‐chloromethyl‐4‐fluoro‐1,4‐diazoniabicyclo[2.2.2]octane bis‐tetrafluoroborate (F‐TEDA) to unsaturated systems was modelled computationally at the ab initio levels and studied experimentally. The reaction of olefins with F‐TEDA is driven exclusively by charge transfer and displays the antibonding orbital picture in the transition structure for F‐transfer, similarly to that for the reactions of olefins with F‐radical. In contrast, the electrophilic and concerted fluorinations, respectively with H₂O???F⁺ complex and with F₂, show strong bonding interactions between the fluorine and olefin moieties in the transition structures. The reaction with F‐TEDA involves an initial formation of highly delocalized charge‐transfer complexes in the first step with further low‐barrier (ca 4 kcal) migration of fluorine and is best described as an inner‐sphere electron transfer. This nonelectrophilic mechanism is operative for the transannular addition of F‐TEDA to 3‐methylene‐7‐ethylidenebicyclo[3.3.1]nonane studied experimentally. The addition mode is determined by the formation of a more stable complex via the ethylidene fragment and demonstrates selectivities that differ from conventional electrophilic additions. This mechanistic scenario may be extended to the fluorination with xenon difluoride where similar products are formed in high yields. Copyright © 2010 John Wiley & Sons, Ltd.     

Feature of the magnetotransport of a quasi-one-dimensional electrons on the superfluid helium

The magnetotransport in a nondegenerate quasi-one-dimensional (Q1D) electron system over superfluid helium has been investigated experimentally. The measurements are performed in the presence of a perpendicular magnetic field B up to 2.6 T in the temperature range T=0.48–2.05 K in the system of conducting channels of 100–400 nm width. It is shown that the value of longitudinal magnetoresistance ρ_xx increases with B. In the electron-gas scattering region (T>0.9 ), the behaviour of ρ_xx agrees with classical Drude law. In the quantum transport regime, the self-consistent Born approximation (SCBA) theory for a 2D electron system over liquid helium describes the experimental data qualitatively. The deviation due to the difference of the experimentally studied Q1D system of the electrons in a parabolic potential well differs from theoretically analysed one. The experimental data agree with the theoretical calculation for the Q1D electron system at the weak magnetic field and the low temperature.

The negative magnetoresistance of the conducting channels has been observed in both the gas- and the ripplon-scattering region. These effects have been explained by weak carrier localization on the gas atoms at high temperature and by display of the quantum magnetotransport features in a mesoscopic system at low temperature.     

Anomalous behavior of conductivity of the confined Q1D electron system over liquid helium

Conductivity of electrons in a quasi-one-dimensional (Q1D) system over liquid helium in narrow channels with the parabolic profile of the potential well has been investigated at temperature T, from 0.4 to 1.8 K, for different driving electric fields and radius of channel curvature. The interval of linear electron densities varied from 2.18×10³ up to 1.7×10⁶ cm⁻¹.

The inverse mobility (1/μ_eff) in the electron-ripplon scattering region at the high linear densities of charges in the channel increases with temperature decreasing. This anomalous behavior of the electron transport in the low-temperature region has been explained by either the electron ordering or the polaronic effects in confined conducting channels. The nonlinear behavior of the electron velocity as a function of a driving electric field is supposed to be due to Breg–Cherenkov radiation of the ripplons. The radiation occurred if the velocity of electrons in the channel approaches to the critical value.     

Model for the dynamics of two interacting axisymmetric spherical bubbles undergoing small shape oscillations

Interaction between acoustically driven or laser-generated bubbles causes the bubble surfaces to deform. Dynamical equations describing the motion of two translating, nominally spherical bubbles undergoing small shape oscillations in a viscous liquid are derived using Lagrangian mechanics. Deformation of the bubble surfaces is taken into account by including quadrupole and octupole perturbations in the spherical-harmonic expansion of the boundary conditions on the bubbles. Quadratic terms in the quadrupole and octupole amplitudes are retained, and surface tension and shear viscosity are included in a consistent manner. A set of eight coupled second-order ordinary differential equations is obtained. Simulation results, obtained by numerical integration of the model equations, exhibit qualitative agreement with experimental observations by predicting the formation of liquid jets. Simulations also suggest that bubble-bubble interactions act to enhance surface mode instability.     

Shallow Donors and Deep-Level Color Centers in Bulk AlN Crystals: EPR, ENDOR, ODMR and Optical Studies

The results of studies of shallow donors and deep-level color centers in bulk AlN crystals are presented. Two shallow donors (presumably oxygen located on the nitrogen site and carbon located on the aluminum site) are suggested to exhibit the DX-relaxation. Third shallow donor (presumably silicon on the Al site) shows the shallow donor behavior up to the room temperature and can be observed without light excitation at temperatures above 200 K. The values of the Bohr radius of the shallow donors are estimated. The structure of deep-level color centers (neutral nitrogen vacancy V _N) in bulk AlN crystals is determined and analyzed by electron paramagnetic resonance, electron-nuclear double resonance, optical absorption and thermoluminescence induced by X-ray irradiation. Spin-dependent recombination processes in AlN crystals are studied by means of optically detected magnetic resonance.