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.     

Elastic properties of liquid crystals

The structural and elastic properties of 4-n′-pentyl-4′-cyanobiphenyl (5CB) in the nematic liquid-crystal phase are investigated in the framework of the statistical-mechanical theory and the molecular dynamics method.     

Critical behavior in the vicinity of nematic to smectic A (N–SmA) phase transition of two polar–polar binary liquid crystalline systems

Phase diagram, critical behavior and order of the nematic (N)–smectic A (SmA) phase transition of two polar–polar binary systems (i) 4-n-heptyloxy-4′-cyanobiphenyl (7OCB) and 4-n-octyloxy-4′-cyanobiphenyl (8OCB); (ii) 4-n-octyloxy-4′-cyanobiphenyl (8OCB) and 4-n-nonyloxy-4′-cyanobiphenyl (9OCB) by means of a high-resolution temperature scanning measurement of birefringence have been reported in this work. A simple power law analysis has been adopted to extract the specific heat critical exponent (α′) at N–SmA transition from birefringence data. The α′ for N–SmA transition indicates a uniform crossover behavior and has appeared to be non-universal in nature. With increasing concentration of the higher homologues for both the binary systems, the N–SmA transition reveals a strong tendency to be driven towards the tricritical nature. The 3D-XY limit (i.e. α′ = ?0.007) for N–SmA transition reaches at the concentration x_8OCB = 0.28 corresponding to the McMillan ratio 0.914, whereas the tricritical point has been found to appear near x_9OCB = 1.0 corresponding to McMillan ratio 0.992.     

Bent-shaped mesogenic oxadiazoles and thiadiazoles with terminal methyl group

Rod-shaped 4-methylbenzoic acid-N′-(4′-n-alkoxybenzoyl) hydrazide (series I) have been synthesized by the Schotten–Baumann reaction of 4-methylbenzhydrazide with 4-n-alkoxy benzoyl chloride using dry pyridine, as a solvent. The series I compounds have been cyclized to bent-shaped mesogenic 2-(4′-methylphenyl)-5-(4″-n-alkoxyphenyl)-1,3,4-oxadiazoles (series II) and 2-(4′-methylphenyl)-5-(4″-n-alkoxyphenyl)-1,3,4-thiadiazole (series III) using POCl₃ and Lawesson's reagent, respectively. The synthesized compounds are characterized by the combination of elemental analysis and standard spectroscopic methods. In series II, lower and middle members are non-mesogenic. n-Dodecyloxy to n-hexadecyloxy derivatives exhibit enantiotropic nematic mesophase. In series III, all the compounds synthesized exhibit enantiotropic nematic mesophase. n-Tetradecyloxy and n-hexadecyloxy derivatives also exhibit enantiotropic SmA mesophase. The mesomorphic properties of the series II and III used in this study are compared with each other and with other structurally related compound to evaluate the effect of different heterocyclic moieties as well as terminal substituents on mesomorphism.     

Effect of aerosil dispersions on the nematic-to-isotropic interface

The effect of silica aerosils on the kinetics of the first-order nematic-isotropic (NI) phase transition is phenomenologically described in the framework of the time-dependent Landau-Ginzburg equation. A steady-state solution to the equation is presented such that the NI interface may propagate with a solitary-like wave profile under constant quenching. The results provide a plausible basis for the interpretation of the dynamical effects of quenched disorder in the liquid-crystal systems, caused by randomly interconnected porous media, such as aerosils. In the low silica aerosil ρ_s ( ≤0.1 g/cm^3) regime, the calculated values of the interface velocity v(T,ρ_s), the interface thickness κ(T,ρ_s), and the critical radius of a spherical nucleus of new nematic phase in a bulk isotropic environment, composed of polar molecules, such as 4-n-octyl- 4^′- cyanobiphenyl and 4-n-heptyl- 4^′- cyanobiphenyl shows that the effect of silica aerosils on the kinetics is reflected in a shifting of the set of temperature-dependent curves to lower temperature values.-1     

Surface tension of free-standing smectic films

A generalized mean-field model, which takes into account the anisotropic interactions between the nearest neighbor molecules (forming free-standing smectic films (FSSFs)) and the stabilizing effect of smectic-air interfaces, has been used for numerically studying the structural and thermodynamic properties of these systems during their layer-by-layer thinning. The results of calculating the surface tension γ of a partially fluorinated liquid-crystal compound formed by 5-n-alkyl-2-(4-n-(perfluoroalkyl-methyleneoxy))pentyl (H10F5MOPP) molecules have demonstrated that the value of γ per FSSF molecule undergoes a stepwise increase during layer-by-layer thinning of the film. The dimensional surface tension during the layer-thinning of a 25 layer FSSF formed by H10F5MOPP molecules varies insignificantly within ∼19 dyn/cm, which agrees with the experimental value (∼14 dyn/cm) for this liquid-crystal compound.     

Twisted-grain-boundary (TGB) phases: nanostructured liquid-crystal analogue of Abrikosov vortex lattices

Twisted-grain-boundary (TGB) phases shown by some liquid-crystalline materials have properties common to those of both smectic and cholesteric phases. Following analogy between liquid crystals and super conductors proposed by de Gennes [Solid State Commun., 10, 753 (1972)], Renn and Lubensky [Phys. Rev. A, 38, 2132 (1988)] theoretically predicted a chiral analog of the smectic A (SmA*) phase, which is now known as TGBA phase. The TGBA phase was experimentally observed for the first time by Goodby et al. [Nature, 337, 449 (1989)] in the chiral homologous series of ferroelectric liquid-crystal material R- and S-1-methylheptyl 4′-[(4′′-n-alkoxyphenyl)propionoyloxy]-biphenyl-4-carboxylates (nP₁M₇), with n?=?13,14,15. Since then, more than a hundred pure and mixed systems showing TGBA phase have been found. Later, Renn derived a mean-field phase diagram based on the chiral Chen-Lubensky model, and predicted two more TGB phases, namely TGBC and TGBC?. These two phases have also been experimentally observed in many systems, and in a few, the phase diagram is similar to that predicted by Renn. Unlike the TGBA phase, several theoretical models have been proposed for TGBC and TGBC? phases, and it remains to be ascertained whether all the types of proposed TGBC/TGBC? structures experimentally exist. A review of the theoretically predicted and experimentally observed TGB phases is given in the present article. Some recently observed novel optical textures of the TGB phases are also reported.     

Induced Smectic-G Phase Through Intermolecular Hydrogen Bonding,Part XIII: Impact of a Nematogen on Phase Behaviour of Hydrogen-Bonded Liquid Crystals

A series of hydrogen-bonded mesogens, p-( p′-methoxybenzylidene)-cyanoaniline:p-n-alkoxybenzoic acids (MBCA:nABA), is synthesised by using liquid-crystalline p-n-alkoxybenzoic acids (nABA) (where n represents alkoxy carbon numbers, 3-10 and 12) and a nematogen, p-( p′-methoxybenzylidene)-cyanoaniline (MBCA). The thermal and phase behaviour of these compounds is studied by thermal microscopy (TM) and differential scanning calorimetry (DCS) techniques. These studies reveal the induction of smectic-G phase in all the compounds. The structural elucidation pertaining to the formation and stabilisation of intermolecular hydrogen bonding is carried out by a detailed IR spectral investigation. The impact of imino group of the nematogen, MBCA, on the liquid-crystallinity of the present series is realised from the comparative studies made on the reported analogous series, p-aminobenzonitrile:p-n-alkoxybenzoic acids (ABN:nABA).     

Characterization of the smectic-A-hexatic-B transition in 65OBC by adiabatic scanning calorimetry

We investigated the smectic-A-hexatic-B (SmA-HexB) transition in the liquid-crystal n-hexyl-4-n-pentyloxybiphenyl-4-carboxilate (65OBC) with adiabatic scanning calorimetry. We were able to prove in a direct way that this transition is indeed very weakly first order, as was already suggested in the literature. The latent heat at the transition was determined to be H_L = 0.04±0.02 J/g. Our experiments confirm the high value for the heat capacity critical exponent earlier reported, yielding = 0.64±0.05.     

Inverse regime of ionic modification of surface anchoring in nematic droplets

It was found that the effect of the ionic modification of anchoring in liquid-crystal droplets can be implemented in the inverse regime. Droplets of 4-n-pentyl-4′-cyanobiphenyl nematic doped with ionic cetyltrimethylammonium bromide surfactant were dispersed in polyvinyl alcohol and investigated. In the initial state, nematic droplets have a radial structure with homogeneous homeotropic anchoring typical of the surfactant used. In the presence of a dc electric field, the boundary conditions become tangential in the surface area left by the cations. That results in the transformation of an orientational structure following by various scenarios. For the new states of nematic droplets, the distribution of the director field was analyzed and the corresponding textural patterns were numerically calculated.     

Dipole moment and mobility of molecules in nematic liquid crystals of the 4-n-butyl ester of [4′-n-hexyloxyphenyl] benzoic acid in the absence of external orienting fields

Dielectric polarization was studied in a nematic liquid crystal of the 4-n-butyl ester of [4′-n-hexyloxyphenyl] benzoic acid (BE[HOP]BA) in the absence of external orienting fields in the isotropic and mesophase states in a frequency range of 10³–10⁷ Hz. In the isotropic melt, three regions of dielectric absorption of a relaxation origin were revealed. It is shown that two of them are related to a reorientation motion of individual molecules about the longitudinal axes (process I) and about the short axes (process II). Processes I and II have relaxation times τ ～ 10^?9 and 10^?8 s and activation energies ΔU ～ 16 and 23 kcal/mol, respectively; the energy of activation of process II in the liquid-crystal phase increases to ΔU ～ 38 kcal/mol. In the isotropic melt, in addition to processes I and II, process III occurs in the low-frequency range, which is characterized by greater relaxation times τ ～ 10^?7 s and an activation energy ΔU ～ 28 kcal/mol. In order to establish the nature of process III, temperature dependences of the dipole moments and Kirkwood correlation factor g were studied in both BE[HOP]BA phases. The magnitude of the Kirkwood factor in the isotropic phase of the BE[HOP]BA near the transition temperature from the mesomorphic state (g ～ 0.88) indicates the retention of the orientational ordering of molecules of the low-molecular liquid crystal and the compensation of their dipole moments intrinsic to the liquid-crystal state. This circumstance suggests that the third process of the relaxation of dipole polarization is due to a cooperative mode of motion of molecules in mesophase nuclei in the isotropic melt.     

向列相液晶$lt;i$gt;n$lt;/i$gt;CB(4-$lt;i$gt;n$lt;/i$gt;-alkyl-4′-cyanobiphenyls, $lt;i$gt;n$lt;/i$gt;=5—8)的旋转黏度及其奇偶效应的分子动力学模拟

在全原子力场模型的基础上,对向列液晶nCB（4-n-alkyl-4′-cyanobiphenyls, n=5—8）进行了等压等温NPT系综下的分子动力学（MD）模拟.对MD的轨迹分析得到了二阶和四阶序参数以及描述液晶分子翻转运动的取向时间相关函数（TCF）,并通过一个近似的单指函数对TCF拟合得到了相关时间.在此基础上,计算了nCB（n=5—8）的旋转扩散系数（Rotational diffusion coefficient, RDC）.利用基于统计力学模型的Nemtsov-Zakharov方法和Fialkowski方法,分别计算了它们的旋转黏度系数（rotational viscosity coefficient, RVC）,进而分别讨论了RVC,RDC和相关时间的奇偶效应.与文献中的实验结果比较表明,该方法得到了合理的计算结果和一致的奇偶效应. 关键词： 旋转黏度 奇偶效应 分子动力学模拟 向列相液晶     

Dielectric permittivity studies of nematogenic compounds and their binary mixtures showing induced smectic Ad phase

The binary mixture of 4-n-pentyl phenyl 4-n′-hexyloxy benzoate (ME6O.5) and p-cyanophenyl trans-4-pentyl cyclohexane carboxylate (CPPCC) shows the presence of induced Smectic A_d phase. In the present work the phase diagram as well as static dielectric permittivity measurements of different mixtures throughout the composition range, are reported. The observed variation of dielectric anisotropy with molar concentration in the nematic and smectic phases is explained, assuming the formation of both homo- and hetero-dimers in the mixture.     

Phase behavior of four homologous compounds of 4-n-alkyl-4′-isothiocyanatobiphenyl (nBT) under pressure

The phase behavior of four homologous compounds of 4-n-nonyl-, 4-n-decyl-, 4-n-undecyl-, and 4-n-dodecyl-4′-isothiocyanatobiphenyl (9BT, 10BT, 11BT, and 12BT) was reinvestigated to characterize their high-pressure mesophases under pressures up to 150 MPa using a polarizing optical microscope equipped with a high-pressure optical cell and a wide-angle X-ray diffractometer equipped with a high-pressure sample vessel. The pressure-induced mesophases of 9BT and 10BT appearing under pressures above about 60 and 100 MPa, respectively, were identified as nematic (N) and smectic A (SmA) phases, which indicate the reversible Cr–CrE–N–I and Cr–CrE–SmA–I phase transitions under elevated pressure. Both the 11BT and 12BT exhibited the reversible transition of Cr–CrE–SmA–I in the low-pressure regions below about 5 and 23 MPa, respectively. Both the stable CrE phases changed into the monotropic (and metastable) one under higher pressures, which the Cr–SmA–I and I–SmA–CrE–Cr phase transitions on heating and cooling processes were recognized, respectively.     

Distribution function of relaxation times for a 4-<Emphasis Type="Italic">n</Emphasis>-pentyl-4′-cyanobiphenyl liquid crystal

The distribution function of relaxation times is reconstructed from the dielectric loss spectrum measured over a wide range of frequencies for a 4-n-pentyl-4′-cyanobiphenyl (5CB) liquid crystal. It is demonstrated that the distribution function for the isotropic and nematic phases is asymmetric in shape. Comparison shows that the reconstructed distribution function is in qualitative agreement with similar functions that are analytically derived from the Cole-Davidson and Havriliak-Negami empirical equations. The specific features observed in the behavior of the distribution function with a variation in the angle between the direction of polarization of a microwave electric field and the director of the liquid-crystal molecules are analyzed. A complex dependence of the permittivity for the liquid crystal in the range of ultrahigh frequencies is explained in terms of additional relaxation mechanisms associated with different motions of molecular fragments of alkyl chains.     

N.M.R. spectra of oriented molecules

By analysis of the high resolution N.M.R. spectrum of 1,2,2,3-tetrachloro-propane partially oriented in a liquid-crystal solvent, it has been shown that this molecule takes up predominantly the G′G′ type of conformation.     

Phase behavior of four homologous compounds of 4-n-alkyl-4′-isothiocyanatobiphenyl (nBT) under pressure

The phase behavior of four homologous compounds of 4-n-nonyl-, 4-n-decyl-, 4-n-undecyl-, and 4-n-dodecyl-4′-isothiocyanatobiphenyl (9BT, 10BT, 11BT, and 12BT) was re-investigated to characterize their high-pressure mesophases under pressures up to 150 MPa using a polarizing optical microscope equipped with a high-pressure optical cell and a wide-angle X-ray diffractometer equipped with a high-pressure sample vessel. The pressure-induced mesophases of 9BT and 10BT appearing under pressures above about 60 and 100 MPa, respectively, were identified as nematic (N) and SmA phases, which indicate the reversible Cr–CrE–N–I and Cr–CrE–SmA–I phase transitions under elevated pressure. 11BT and 12BT exhibited the reversible transition of Cr–CrE–SmA–I in the low-pressure regions below about 5 and 23 MPa, respectively. Both the stable CrE phases changed into the monotropic (and metastable) one under higher pressures, in which the Cr–SmA–I and I–SmA–CrE–Cr phase transitions on heating and cooling processes, respectively, were recognized.     

Angular tuning of defect modes spectrum in the one-dimensional photonic crystal with liquid-crystal layer

A one-dimensional ZrO₂/SiO₂ photonic crystal with a 4-n -pentyl-4' -cyanobiphenyl (5CB) nematic defect layer was used to investigate the transmission spectra of light polarized parallel and perpendicular to the liquid-crystal director at different angles of incidence. The spectra of the photonic crystal were shown to split into four polarized components T_ij at oblique incidence. When the incident angle increased, the bandgap edges and the defect modes shifted towards short wavelengths, while the amplitudes of the defect modes increased for the transverse magnetic polarization and decreased for the transverse electric polarization. The observed discrepancy between the defect mode amplitudes in the center and near the edges of the photonic bandgap was found to be related to the radiation losses inside the defect layer of a non-ideal photonic crystal. The simulated transmission spectra obtained using recurrence relations and taking into account the decay of defect modes are in good agreement with the experimental data.     

Electro-optic and viscoelastic properties of a ferroelectric liquid crystalline binary mixture

ABSTRACT

This study describes the properties of a binary liquid crystalline mixture composed of commercially available materials, Ce-3 (4-(n-hexyloxy phenyl)-1-(2-fuethyl butyl) biphenyl-4-carboxylate) and Ce-8 (4-(2-methylbutyl) phenyl-4-n-octylbiphenyl-4-carboxylate), in a weight ratio of 50:50. Both compounds show polymesomorphism and ferroelectric properties within a relatively wide temperature range. Taken separately, each compound has its advantages and disadvantages from the technical point of view. The influence of temperature on the electro-optical and viscoelastic properties of the produced binary mixture is investigated in this paper.     

Characteristics of the formation of radiation defects in silicon structures

The method of deep-level transient spectroscopy is used to investigate aspects of the formation of radiation defects in silicon p ⁺-n diffusion structures when bombarded by accelerated electrons. It is shown that for base thicknesses of the p ⁺-n structures in the range 0.2–0.6mm a substantial change in the concentration of the radiation defects formed in this way is observed, having a maximum at 0.25 mm. Below 0.2 mm and above 0.6 mm the concentration of radiation defects exhibits a weak dependence on base thickness. The observed effect is explained by variation of the relative concentrations of vacancies and interstitial silicon atoms in the base during formation of p ⁺-n pairs. Zh. Tekh. Fiz. 69, 121–123 (January 1999)