Optical activity measurements in the smectic blue phases

Optical activity measurements have been performed on the smectic blue phases ( BP _Sm), which are a new kind of chiral liquid crystal. BP _Sm exhibit both three-dimensional orientational order, like the classical blue phases, and smectic positional order. Thus, they can be viewed as the three-dimensional counterpart of the twist grain boundary phases. A comparison with the optical activity of the classical blue phases is carried out, and an estimation of the BP _Sm lattice parameter is reported for the first time. Received 25 May 2001     

Molecular structure and physical parameters of some ferroelectric liquid crystal systems

We investigate thermodynamic properties and spontaneous polarization of ferroelectric liquid crystal (SmC^*LC) systems: smectic C matrix + chiral adding (ChA). The fact of existence of an optimum concentration of ChA, for which the studied SmC^*LC systems have the maximum value of spontaneous polarization, and a certain concentration, at which the phase transition of the chiral tilted smectic C phase to the smectic A phase occurs, is established. Temperature dependence curves for the free energy, configuration energy, specific heat, and the orientational order parameter are calculated in the temperature range of existence of liquid crystal mesophases. The curves are in good agreement with the experimentally observed trends of the SmC^*LC properties.     

铁电液晶螺旋结构的理论近似研究

由铁电液晶（FLC）手性近晶C相下螺旋结构的理论近似计算得出FLC一个螺距内平均折射率的表达式,根据表达式可得出一个螺距内的FLC分子作为一个整体可以看成一个向列相液晶分子模型的结论.当FLC沿螺旋轴方向的厚度等于FLC螺距的整数倍时,液晶盒内垂直取向的FLC分子可看作向列相液晶模型组成的集合.ZLI-3654型FLC与5CB型向列相液晶的实验结果验证了上述结论,理论结果和实验结果一致.这一理论可为畸变螺旋FLC和垂直排列畸变螺旋FLC器件的制备以及FLC的应用提供理论指导和更深的认识. 关键词： 铁电液晶 螺距 平均折射率 向列相液晶     

Phase transitions in nanocomposites of hydrogen-bonded dimeric liquid crystals with mesogenic and non-mesogenic components

Microtextural polarization, phase transitions, and electro-optical effects are studied in a series of nanocomposites, grown by mixing alkyloxybenzoic acids (nOBAs), displaying hydrogen-bonded dimeric liquid crystal (LC) state, with non-mesogens (single-walled carbon nanotubes (SWCNTs), perfluorooctanoic acid) or mesogens (bent-core LC compound D14F3). Each of the studied nanocomposites, in which the nOBA serves as a matrix, forms complexes with bent-shaped dimeric, caused by the interaction between the dopant structural units and the dimer rings. This feature, coordinated with the surface anchoring, bulk and electrical effects, leads to drastic reduction of the LC system symmetry. As a result, transitions from achiral (characteristic for the pristine nOBA) to chiral states (including ferroelectric smectic C with C₂ symmetry and ferroelectric smectic C_G with the lowest C₁ triclinic one) take place. The functionalization of the SWCNTs causes drastic increase of the ferroelectricity.     

Discontinuity walls terminated by twist disclinations in smectic a liquid crystals

A discontinuity wall in smectic A liquid crystals was discussed in M. Kléman:Points, Lines and Walls in Liquid Crystals, Magnetic Systems and Various Ordered Media (J. Wiley, Chichester, 1983). Possible solutions describing a singularity — twist disclination which terminates the discontinuity wall in an infinite model smectic A liquid crystal are discussed. One of solutions proposed can be used to describe the so-called zigzag defect line in chiral smectic C liquid crystals on which opposite oriented chevrons are terminated. This work was supported by Grant No.: 202/96/1687 of the Grant Agency of the Czech Republic.     

Measurements of absolute values of electrooptic coefficients in a ferroelectric liquid crystal

Weak external electric field E causes two effects in chiral smectic liquid crystals: linear change of the optic axis direction and modification of the shape of the indicatrix. The relative changes in the light intensity consist of two components. The first component represents the modulation with the fundamental frequency f and the second one, with the doubled frequency 2f (second harmonic). We carried out measurements of the electrooptic modulation at both the first and second harmonics frequency. The applied calibration procedure allowed for expressing the experimental results as angular quantities independent of experimental conditions. Therefore we were able to determine the absolute values of the coefficients describing both effects of the electric field on the optical properties of the sample. We studied the temperature dependence of the first and second order coefficients in the ferroelectric smectic C? and paraelectric smectic A phases. The experiments delivered an information on the structure of tilted smectic liquid crystals and its dependence on the electric field.     

X-ray investigation of dialkyldimethylammonium bromides

Abstract

A Series of dialkyldimethylammonium bromides (DDAB), (C _n H_2n+1)zN⁺(CH₃)₂Br^?with n = 10, 12, 14, 16 and 18 were investigated using X-ray diffraction. Measurements were performed by the photographic Guinier method as well as by diffractometer on samples aligned on a glass substrate. For a sample with n=12, X-ray high-pressure measurements were also performed which allowed us to confirm the destabilization under pressure of the phase existing on heating above the first transition point. For all the studied compounds, except for that with n =16, strong hysteresis and rich polymorphism were observed. A smectic T phase - high-temperature liquid crystal was confirmed for compounds with n= 16 and 18. All the remaining alkylammonⁱum salts have smectic an E high-temperature liquid crystal phase.     

Clark–Lagerwall effect in the small particles—Ferroelectric liquid crystal system

The smectic C* based on a three-component mixture of liquid crystals (LC) with not mesogene chiral additive and showing ferroelectric properties has been developed. The physical parameters which are responsible for electrooptical effects are defined. The Clark–Lagerwall effect both in the pure smectic C* and with the additive of small particles of the centrosymmetric substance Al₂O₃ and the ferroelectric SrTiO₃ is investigated. It has been shown that time characteristics of a cell with LC-Al₂O₃ are a little bit worsened in comparison with a cell with pure LC. It is caused by increase of the rotational viscosity of the ferroelectric liquid crystal with addition of small particles Al₂O₃. Time characteristics of the Clark–Lagerwall effect in the LC-SrTiO₃ cell essentially surpass time characteristics of the cell with pure LC because the transition from the deformed UP-state to the DOWN-state demands overcoming much lower energy than the transition from the pure UP-condition to the DOWN-state.     

Design, synthesis and characterization of a linear hydrogen bonded homologous series

A linear hydrogen bonded liquid crystalline homologous series has been synthesized and characterized. Hydrogen bond is formed between p-n-dodecyloxy benzoic acid and various p-n-alkyl benzoic acids whose alkyl chain vary from octyl to ethyl. Synthesized complexes are characterized by FTIR, ¹H NMR and ¹³C NMR studies for inferring the formation of hydrogen bonds. Polarizing Optical Microscopy (POM) and DSC studies reveal various mesophases and their corresponding transition temperatures along with respective enthalpy values. All the seven synthesized complexes exhibit rich liquid crystalline mesomorphism. A new phase namely smectic X has been observed in five of the complexes with a narrow thermal range. This phase has been characterized by optical textural, DSC, tilt angle and helicoidal pitch studies. Smectic X is sandwiched between traditional smectic C and re-entrant smectic C (designated as C_R) phases. Homeotropic transition in nematic phase is observed in all the mesogens and thus these materials can be used as thermally controlled optical shutters. Tilt angle in smectic C, smectic X and smectic C_R phases have been experimentally elucidated for all the mesogens.     

Influence of silica nanoparticles on dielectric spectroscopy and polarization switching responses of novel ferroelectric liquid crystals

Silica (SiO₂) nanoparticles in different wt/wt% ratios were dispersed in a novel room temperature ferroelectric liquid crystal mixture. Dielectric relaxation spectroscopy (50 Hz–1 MHz) and electro-optic responses were investigated. Dielectric permittivity gradually decreases by about 40% up to 1 kHz with increasing SiO₂ concentration in the chiral smectic C phase. However, an increase of up to 1.5% has been observed for all the silica-doped samples above 2 kHz. We noticed an increase in optical transmission with increasing SiO₂ concentration from 0.01 to 0.1 wt/wt%.     

Theoretical investigation of antiferroelectric (SmCA) subphases by hydrodynamical approach

We provide a hydrodynamical approach utilizing time dependent Landau-Ginzburg model (L-G) and the Cahn-Hilliard model (C-H) to investigate antiferroelectric liquid crystals (AFLCs) exhibiting different chiral phases between paraelectric smectic A (SmA^?) phase and antiferroelectric smectic C_A^? phase (SmC_A^?). Introducing conserved and non-conserved order parameters in C-H and L-G models, we have predicted the appearance of a chiral smectic C (SmC^?) phase and a ferrielectric SmC_FI1^? phase (three layers SmC_A^?) in an antiferroelectric phase sequence. The three layers periodicity for SmC_FI1^? phase is studied in detail with a non-uniform layer interactions among smectic layers with strong experimental support. Finally, we provide some theoretical basis for the non-uniformity of our proposed layer interactions.     

Dielectric and calorimetric studies on 1BC1EPOPB feroelectric liquid crystal having a large spontaneous polarization

Experimental investigations on the ferroelectric liquid crystal, R-4′(1-butoxycarbonyl-1-ethoxy) phenyl 4-(4-octyloxy phenyl) benzoate (1BC1EPOPB) of large spontaneous polarization (P _S(+) = 240?nC?cm^?2), using dielectric and calorimetric techniques, are reported. The temperature range of 25.0–125.0°C has been chosen for dielectric measurements. Dielectric dispersion studies are carried out in the temperature range 45.0–75.0°C and in the frequency range 2?Hz to 2?MHz for the smectic A, smectic C* and smectic X phases. A new phase called ‘smectic X’ has been found around 56.3°C. The transition temperatures identified by the dielectric dispersion studies for different phases and those given by DSC techniques are in close agreement.     

Viscoelastic modes in chiral liquid crystals

Viscoelastic properties of liquid crystals are very important for applications like display technology. However, there are not many direct techniques to study them. In this review, we describe our studies on the viscoelastic modes of some chiral liquid crystals using dynamic light scattering. We discuss viscoelastic modes corresponding to the C director fluctuations in the chiral smectic C phase and the behaviour of the Goldstone-mode near the chiral smectic C-smectic A phase transition. In cholesteric liquid crystals, we consider the director fluctuations in a wavevector range comparable to the inverse pitch of the cholesteric. Here, the study of the scattered light in the vicinity of the Bragg reflection using a novel geometry will be presented.     

西佛碱型液晶化合物相变过程中分子排列方式变化的拉曼光谱研究

用变温拉曼光谱对相变过程的研究表明,液晶化合物的初始晶态与熔融后缓慢降温得到的晶态并不吻合,两个状态下分子尾链的构象及刚性核部分的构象不同导致分子的聚集状态不同。西佛碱型液晶化合物VO10相变过程中,在晶态到液晶态相转变过程中,烷氧基尾链链内构象发生突变,同时有序性降低,刚性核部分两个苯环之间的二面角在相变点时发生明显变化,二面角加大。     

Influence of pressure on the electric-field-induced phase transitions in liquid crystals

Within the framework of Landau-de-Gennes formulation, we analyse the effect of pressure on electric-field-induced phase transitions in a liquid crystal which shows spontaneously an isotropic-smectic A transition. Inferring from the experimental pressure dependences on the layer spacing in smectic A phase, as well as the nematic-smectic A metastable temperature T^*_AN, we incorporated the pressure dependence in the free energy through (the surface energy term) and the coupling between the quadrupolar nematic ordering Q_ij and the smectic order parameter ψ. From the S-T phase diagram, we found that the stability of field-induced nematic phase increases with pressure, whereas the discontinuity of the transition decreases. Also, the region where paranematic phase transits directly to smectic A phase increases with pressure.     

The Phase Transitions from Chiral Nematic Toward Smectic Liquid Crystals

A Chen-Lubensky energy is used to investigate phase transitions from chiral nematic to smectic C* and smectic A* liquid crystal phases. We consider a liquid crystalline material Ω confined between two parallel plates, where the dimensions of Ω are assumed to be large relative both to the width of a smectic layer and the material’s chiral pitch. We take boundary conditions so that the smectic phase melts at the plates’ surfaces and prove the existence of energy minimizers in an admissible set consisting of order parameters and molecular directors . Then under the physically observed assumption that the Frank elasticity constants become large near a phase transition, we establish estimates for the transition region separating phases. In particular we derive analytic estimates proving that chirality lowers the transition temperature regime above which minimizers are nematic and below which minimizers are in a smectic phase.Research supported by NSF grants DMS-0306516 and DMS-0456286.     

Effect of chiral solute on the smectic a to C phase transition of second order

The Landau theory is applied to explain the helicoidal effect of a chiral solute on an ordinary smectic C state below a smectic A-C phase transition of second order. It is shown that T_c increases with the concentration c of the solute, for small c. We suggest that a simultaneous application of electric and magnetic fields perpendicular to the smectic layers might, in some cases, also make the C phase helicoidal.     

Specific features of photoisomerization of provitamin D 3 in a nematic liquid crystal

Photoisomerization of provitamin D ₃ (7-dehydrocholesterol) in a nematic liquid crystal (ZLI-1695, Merck) is investigated in detail by UV absorption spectroscopy. It is found that dissolution of chiral molecules of provitamin D ₃ induces the cholesteric phase in a nematic. The spectral kinetics of photoisomerization in this phase changes significantly from that in an ethanol solution. A sharp nonmonotonic dependence of the increase in accumulation of trans isomer tachysterol in a liquid crystal matrix with a decrease in the induced cholesteric pitch from 2200 to 25 μm is revealed.     

Two-stage crystallization on the surface of smectic nanofilms

The influence of the surface and finite size on crystallization in nanofilms of a smectic C liquid crystal with thicknesses between two and several tens of molecular layers has been studied. Transitions in a single surface molecular layer have been detected by optical methods. It has been found that transitions on the film surface take place at a temperature 8°C higher than the crystallization temperature in a bulk sample. Two-stage crystallization has been detected in surface layers where the surface induces a transition to an intermediate structure different from the structure of the phases of the bulk sample.