Esters of 4-nitrocinnamic acids and 4-halogene-4’-hydroxyazobenzenes – synthesis,mesogenic and optical studies

Six new compounds were synthesized that have no alkyl chains in their structure: 4-nitrocinnonates of 4-hydroxyazobenzene, 4-nitro-4’-hydroxyazobenzene, 4-fluoro-4’-hydroxyazobenzene, 4-chloro-4’-hydroxyazobenzene, 4-bromo-4’-hydroxyazobenzene and 4-iodo-4’-hydroxyazobenzene. Using the polarizing microscopy and differential scanning calorimetry, enthalpies and temperatures of phase transitions were determined. All investigated compounds have an enantiotropic nematic phase. These compounds proved to be extremely thermally stable. Thermal decomposition was observed in temperatures above 300°C. Investigated compounds contain two different chromophore groups (i.e. azo and ethene moieties), which influenced the complex trans–cis isomerization processes of both groups (three time-separated processes were observed). It was shown that the presence of the ethene group significantly shifts the π-π* band towards higher energies. The substituent polarity in the azo group also affected the energy of this absorption band. A weak luminescence effect was observed in the 4-nitrocinnonates of 4-hydroxyazobenzene compound.     

Pretransitional dielectric properties of nematogenic 4-cyanophenyl-4′-n-heptylbenzoate

This article presents results of the static and dynamic dielectric studies performed for mesogenic 4-cyanophenyl-4′-n-heptylbenzoate in the isotropic (I) and nematic (N) phases. Pretransitional phenomena are observed in the vicinity of I–N phase transition as an anomalous temperature behavior of both the static and the dynamic dielectric properties of the compound. The temperature dependence of the static permittivity is correlated with the entropy change induced by the probing electric field while an anomalous behavior of the dielectric relaxation directly points out for a subdiffusional Brownian rotation of mesogenic molecules in the vicinity of the phase transition.     

Dielectric properties of 4′-n-alkyl-4-cyanobiphenyls in their nematic phases

The principal dielectric constants of the pentyl to octyl derivatives of 4′-n-alkyl-4-cyanobiphenyl have been measured as functions of temperature in their nematic and isotropic phases. All the compounds exhibit a strong positive dielectric anisotropy due to the presence of a large dipole moment along the major molecular axis. The principal dielectric constantsε _‖ andε _⊥ as well as the anisotropy Δε decrease with increasing alkyl chain length. The experimental value of (ε_‖+2ε_⊥) decreases with decreasing temperature, and is throughout less than the extrapolated isotropic value, in conformity with the model of antiferroelectric short range order proposed by Madhusudana and Chandrasekhar.     

Optical and dielectric properties of the mesogen 4-cyano-4′-n–octyl biphenyl as a function of temperature

The effect of temperature on certain optical and dielectric properties of one member, namely 4-cyano-4′-n–octyl biphenyl (8CB) of the mesogenic series 4-cyano-4′-n–alkyl biphenyl (nCB), is reported. The dependence of the ordinary and extraordinary components of polarisability, α_o and α_e, on temperature is studied using a He–Ne laser beam, and the variation of orientational order parameter with temperature in the entire mesogenic phase determined from the optical studies. The dependence of the effective molecular dipole moment, μ_eff, in the liquid-crystal phase, and the angle of inclination, β, of the dipole moment with the preferred direction have been investigated. An experimental estimate of the correlation factor ‘g’, which is indicative of the nature of the molecular association in the mesophase, has been obtained.     

Enhancement of electronic,photophysical and optical properties of 5,5′-Dibromo-2,2′-bithiophene molecule: new aspect to molecular design

The aims of this study were to enhance electronic, photophysical and optical properties of molecular semiconductors. For this purpose, the isomers of the B-doped molecule (5,5′-Dibromo-2,2′-bithiophene) have been investigated by density functional theory (DFT) based on B3LYP/6-311++G** level of theory. The isomers were first calculated using kick algorithm. The most stable isomers of the B-doped molecule are presented depending on the binding energy, fragmentation energy, ionization potential, electron affinity, chemical hardness, refractive index, radial distribution function and HOMO-LUMO energy gap based on DFT. Ultraviolet-visible (UV–vis) spectra have been also researched by time-dependent (TD) DFT calculations. The value of a band gap for isomer with the lowest total energy decreases from 4.20 to 3.47 eV while the maximum peaks of the absorbance and emission increase from 292 to 324 nm and 392 to 440 nm with boron doped into 5,5′-Dibromo-2,2′-bithiophene. Obtained results reveal that the B-doped molecule has more desirable optoelectronic properties than the pure molecule.     

Moessbauer study and magnetic properties of electrochemical material LiFePO4

Magnetic properties and crystal symmetry of electrochemical material LiFePO4 have been investigated by Moessbauer spectroscopy and magnetization measurement. Magnetization reveals the antiferromagnetic nature of LiFePO4. Temperature dependence of inverse susceptibility and that of hyperfine field confirm that there is an antiferromagnetic-paraxaagnetic transition at about 50K.     

Structure and properties of laser quenched 4Cr13 steel

The structure and properties of laser quenched 4Cr13 steel were reported. The results show that: (1) Fine martensite is obtained after laser quenching. The highest content of retained austenite in the surface area 10 μm thick of laser hardened zone is 47. 13 percent, but only 3.6 percent of retained austenite is measured inside the laser hardened layer after the surface layer 10μm thick is worn off. (2) The hardness of laser quenched layer is much higher (HV_(0.1) 690) than that of the substrate (HV_(0.1) 237). (3) The wear resistance of laser quenched layer is 3.3 times higher than that of traditionally treated specimen and the corrosion resistance of 4Cr13 steel is also improved greatly by laser quenching.     

Synthesis and spectroscopic studies of 4-Formyl-4′-N,N-dimethylamino-1,1′-biphenyl: The unusual red edge effect and efficient laser generation

The synthesis and photophysics of 4-formyl-4-N,N-dimethylamino-1,1-biphenyl are reported. The emission spectrum in various solvent polarities demonstrates solvatochromism, indicating that the fluorescence originates from an electronically excited species with a strong charge transfer character. The change in [ _max(absorption) – _max(emission)] varies from 1500 cm^–1 inn-heptane to as much as 7500 cm^–1 in acetonitrile. In protic solvents, the unusual excitation energy-dependent steady-state emission (red edge effect), resulting from solvent dielectric relaxation, was observed in media with a low viscosity. The large Stokes-shifted and high-yield fluorescence led to the observation of the efficient lasing action. The frequency tunability of the laser output is strongly solvent dependent, generating a new charge transfer laser dye in the blue-green region.     

Structure and properties of the anions MF4−, MCl4− and MBr4− (M = C,Si, Ge)

Density functional theory (DFT), Møller–Plesset (MP2) and coupled cluster with single and double substitutions including non-iterative triple excitations (CCSD(T)) calculations on the anions MX₄^?, with M = C, Si, Ge and X = F, Cl, Br, show that GeF₄^?, SiCl₄^?, GeCl₄^? and SiBr₄^? prefer a C_2v conformation, but CCl₄^? is an elongated C_3v structure. CBr₄^? has T_d symmetry in MP2, but is slightly more stable in elongated C_3v form with DFT and CCSD(T). GeBr₄^? has T_d symmetry. CF₄^? and SiF₄^? are unstable with respect to loss of an electron. Vertical electron affinities (EAs) are negative also for CCl₄ and SiCl₄, and close to zero for GeF₄ and SiBr₄. Adiabatic EAs range from 0.47 eV for SiCl₄ to 1.78 eV for GeBr₄. The lowest excited states at T_d symmetry are ²T₂ resonances with energies of 2.1–3.5 eV, resulting from excitation of the a₁ singly occupied molecular orbital to vacant t₂ orbitals. Vertical excitation energies (VEEs) and vibrational frequencies are given for the most stable anionic geometries. Comparison with experimental VEEs for CCl₄^? is made. From dissociation energies of MX₄, MX₄^?, MX₃ and MX₃^?, appearance energies of X^?, MX₃^?, X₂^? and MX₂^? were calculated. Most were found to be in reasonable agreement with experimental values. Theoretical spin densities and g-factors have been compared with experimental results available for CCl₄^?, SiCl₄^? and GeCl₄^?.     

Effects of pressure on structural,electronic, and mechanical properties of α,β,and γ uranium

The first-principles methods have been employed to calculate the structural, electronic, and mechanical properties of the α, β, and γ phases of uranium under pressure up to 100 GPa. The electronic structure has been viewed in forms of density of states and band structure. The mechanical stability of metal U in the α, β, and γ phases have been examined.The independent elastic constants, polycrystalline elastic moduli, as well as Poisson's ratio have been obtained. Upon compression, the elastic constants, elastic moduli, elastic wave velocities, and Debye temperature of α phase are enhanced pronouncedly. The value of B/G illustrates that α and γ phases are brittle in ground state.     

IR spectra temperature changes and conformational structure of 4-butyl-4′-cyanobiphenyl

IR spectra of 4-butyl-4′-cyanobiphenyl in the liquid and solid-crystal states were measured in the 400–4000 cm^–1 region at 28–70°C. Changes of the spectra as a function of temperature are due to the conformational fluxionality of the molecules according to calculated IR spectra of the possible 4-butyl-4′-cyanobiphenyl conformers. Calculations were carried out using the method of fragments and the LEV-100 program package. Bands sensitive to the conformational changes in the molecular structure were found. IR spectra have been interpreted. Conclusions have been made about the conformations of the sample in the solid-crystal and liquid phases. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 3, pp. 325–333, May–June, 2009.     

Structural properties,phase stability,elastic properties and electronic structures of Cu–Ti intermetallics

The structural properties, phase stabilities, anisotropic elastic properties and electronic structures of Cu–Ti intermetallics have been systematically investigated using first principles based on the density functional theory. The calculated equilibrium structural parameters agree well with available experimental data. The ground-state convex hull of formation enthalpies as a function of Cu content is slightly symmetrical at CuTi with a minimal formation enthalpy (–13.861 kJ/mol of atoms), which indicates that CuTi is the most stable phase. The mechanical properties, including elastic constants, polycrystalline moduli and anisotropic indexes, were evaluated. G/B is more pertinent to hardness than to the shear modulus G due to the high power indexes of 1.137 for G/B. The mechanical anisotropy was also characterized by describing the three-dimensional (3D) surface constructions. The order of elastic anisotropy is Cu₄Ti₃ > Cu₃Ti₂ > α-Cu₄Ti > Cu₂Ti > CuTi > β-Cu₄Ti > CuTi₂. Finally, the electronic structures were discussed and Cu₂Ti is a semiconductor.     

Magnetoresistance and magnetic properties of Fe3O4 nanoparticle compacts

In this paper,we report on the magnetic properties of Fe3O4 nanoparticles with different grain sizes under different pressures.In all the samples,the saturated magnetization Ms shows a linear decrease with increasing pressure.The thickness of the magnetic dead layer on the nanoparticle surface nuder different pressures was roughly estimated,which also increases with increasing pressure.The transport measurements of the nanoparticle Fe3O4 compacts show that the low-field magnetoresistance (MR) value is insensitive to the grain size in a wide temperature range;however,the high-field MR value is dependent on grain size,especially at low temperatures.These experimental results can be attributed to the different surface states of the nanoparticles.     

Experimental and theoretical study of the IR spectrum and barriers to internal rotation of 4-hydroxypropyl-4′-cyanobiphenyl

The IR absorption spectrum of polycrystalline 4-hydroxypropyl-4′-cyanobiphenyl is measured in a KBr pellet over the range 400–4000 cm^?1. The structure of the molecule and the frequencies and the intensities of the bands in the spectrum are calculated in the approximation of the B3LYP hybrid density functional with the 6-31 G(d) and 6-31+G(d) basis sets. The normal vibrations are reliably assigned by the method of linear scaling of frequencies, which made it possible to reproduce the experimental IR spectrum with high accuracy. The barriers to internal rotation of phenyl rings and three barriers for the hydroxypropyl radical are calculated.     

Effect of gamma irradiation on the structural,thermal and optical properties of Makrofol BL 2–4

Makrofol BL 2–4 is an extrusion film based on Makrolon polycarbonate. It comprises excellent die-cutting performance combined with high light transmission and moderate light scattering properties. It is a class of polymeric solid state nuclear track detectors which has many applications in various radiation detection fields. In the present work, Makrofol samples were irradiated using different gamma doses ranging from 10 to 350 kGy. The structural modifications in the gamma-irradiated Makrofol samples have been studied as a function of dose using different characterization techniques such as X-ray diffraction, intrinsic viscosity, Fourier transform infrared spectroscopy, thermogravimetric analysis, refractive index and color difference studies. The gamma irradiation in the dose range 20–200 kGy led to a more compact structure of Makrofol polymer, which resulted in an improvement in its thermal stability with an enhancement in its structural and optical properties.     

The centimeter and millimeter microwave spectra of butadiene sulfone and α,α′-D4 butadiene sulfone

Microwave measurements on the ground and first eight excited states of the ring-puckering vibration of butadiene sulfone have been extended to millimeter wavelengths. The microwave spectra of the same vibrational states of α,α′-D₄ butadiene sulfone have been observed. For both isotopomers the Coriolis interaction between the v = 0 and v = 1 states has been analyzed to give the energy separation between these two states. These data and the variation of the rotational constants have been used to derive reduced potential functions for the ring-puckering vibration. The barrier to ring inversion is 49(2) cm⁻¹ for butadiene sulfone and 44(2) cm⁻¹ for the α,α′-D₄ isotopomer. The ring-puckering vibrational dependence of the quartic centrifugal distortion constants, including a small dependence of Δ_J and δ_J, has been accounted for.     

Theoretical investigation of electronic,magnetic, transport and optical properties of the pure and doped cuprate superconductor HgBa2CuO4+δ

We report detailed DFT calculations and Monte Carlo simulations on the pure and doped cuprate superconductor HgBa₂CuO_4+δ. For the pure compound (δ = 0), we have obtained an insulating behavior with strong antiferromagnetic copper spin correlations in the CuO₂ plane. The high value of the calculated Néel temperature T_N = 333 K reflects the large in-plane exchange interaction J = -145 meV. The obtained optical properties and critical exponents demonstrate the anisotropic quasi-2D character of this type of materials. As for the doped compound the electronic structure and the transport properties have been investigated for various values of doping. Based on these data, we suggest a prediction of the value of optimum doping for HgBa₂CuO_4+δ(δ_optimal = 0.125).     

Magnetic, structural, and thermal properties of CoV?O?

In this paper, we investigate the electric, magnetic, structural, and thermal properties of spinel CoV(2)O(4). The temperature dependence of magnetization shows that, in addition to the paramagnetic-to-ferrimagnetic transition at T(C) = 142 K, two magnetic anomalies exist at 100 K, T(1) = 59 K. Consistent with the anomalies, the thermal conductivity presents two valleys at 100 K and T(1). At the temperature T(1), the heat capacity shows one peak, which cannot be attributed to the structural transition as revealed by the x-ray diffraction patterns for CoV(2)O(4). Below the transition temperature T(1), the ac susceptibility displays the characteristics of a glass. The series of phenomena at T(1) and the orbital state on V(3+) sites are discussed.     

Studies on binary mixtures of 4-pentyloxy-4′-cyanobiphenyl with three 4, 4′-di(alkoxy)azoxybenzenes

Eighteen binary mixtures of 4-pentyloxy-4′-cyanobiphenyl (5OCB) and 4, 4′-di(alkoxy)azoxybenzenes (nOAB) with n = 5, 6, and 7 at different concentrations have been studied in detail. Over a wide concentration range, induced SmA phase was observed in all the mixtures except in one. In most of the mixtures, the refractive indices no, ne, and Δn lie between the values of pure components. The optical birefringence of the mixtures is found to decrease non-additively with concentration. The molecular polarizability anisotropy and the orientational order parameter <P₂> of the mixtures were calculated. Nature of variation of polarizability anisotropy with concentration is similar to that of Δn. In allmixtures <P₂> is more in smectic phase than in nematic phase and it also shows non-additive behaviour. Observed <P₂> values of the mixtures were compared with McMillan’s and Maier-Saupe theoretical values and good agreement is found in some mixtures. The transition temperatures obtained by fitting <P₂> data to McMillan’s theory agree with the observed values within a few degrees. Ratio of elastic constants K₃₃ and K₁₁ is determined for mixtures having nematic phase and found to diverge at T_NA transition point.