Frustrated smectic liquid crystalline phases in lactic acid derivatives

ABSTRACT

We have prepared and studied a series of compounds with different types of molecular core and lactate unit in the chiral terminal chain. We draw a survey and comparison of their mesomorphic properties with respect to the occurrence of twist grain boundary (TGB) phases. The materials exhibit extremely wide TGBA phase more than 60K broad, unique TGBA-TGBC-SmC*-SmC_A* phase sequence and unique re-entrant TGBA phase below the SmA phase. TGB phases have been induced in binary mixtures of molecules with different molecular shape and chirality (chiral lactic acid derivative and non-chiral hockey-stick mesogen). Unique effect is observed for compounds with TGBA phase, where the applied electric field transforms the planar texture into the homeotropic one, homogeneously dark in crossed polarizers. The process is analogy of the Frederiks transition so far known only for nematics. This effect, changing the bright state to the dark one, is promising for applications.     

Molecular structure and chiral liquid crystalline phases

We describe briefly some results obtained on both chiral and achiral compounds exhibiting chiral mesophases. We report the first example of a single component system exhibiting the undulated twist grain boundary C* or UTGB _C* phase. Preliminary results concerning a few achiral compounds composed of banana-shaped molecules exhibiting a mesophase is reported. They have been investigated by polarized light optical microscopy, differential scanning calorimetry and x-ray diffraction studies.     

Depletion effects in smectic phases of hard-rod-hard-sphere mixtures

It is known that when hard spheres are added to a pure system of hard rods the stability of the smectic phase may be greatly enhanced, and that this effect can be rationalised in terms of depletion forces. In the present paper we first study the effect of orientational order on depletion forces in this particular binary system, comparing our results with those obtained adopting the usual approximation of considering the rods parallel and their orientations frozen. We consider mixtures with rods of different aspect ratios and spheres of different diameters, and we treat them within Onsager theory. Our results indicate that depletion effects, and consequently smectic stability, decrease significantly as a result of orientational disorder in the smectic phase when compared with corresponding data based on the frozen-orientation approximation. These results are discussed in terms of the τ parameter, which has been proposed as a convenient measure of depletion strength. We present closed expressions for τ, and show that it is intimately connected with the depletion potential. We then analyse the effect of particle geometry by comparing results pertaining to systems of parallel rods of different shapes (spherocylinders, cylinders and parallelepipeds). We finally provide results based on the Zwanzig approximation of a fundamental-measure density-functional theory applied to mixtures of parallelepipeds and cubes of different sizes. In this case, we show that the τ parameter exhibits a linear asymptotic behaviour in the limit of large values of the hard-rod aspect ratio, in conformity with Onsager theory, as well as in the limit of large values of the ratio of rod breadth to cube side length, d, in contrast to Onsager approximation, which predicts τ ∼ d ³. Based on both this result and the Percus-Yevick approximation for the direct correlation function for a hard-sphere binary mixture in the same limit of infinite asymmetry, we speculate that, for spherocylinders and spheres, the τ parameter should be of order unity as d tends to infinity.     

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     

Phase diagrams and dielectric studies of binary mixtures exhibiting intermediate nematic and induced smectic phases

Investigations on the phase diagrams of two bi-component mixtures of liquid crystals are presented. Whereas in one of the bi-component systems, smectic A (SmA) phase is seen to be induced, in the other case the so-called nematic “island” has been observed. The dielectric properties of magnetically oriented sample forming nematic phase and induced smectic phase in one of the mixtures, and a nematic “island” and SmA phase in the other mixture, were measured in the frequency range from 1?Hz to 10?MHz at different temperatures. The transition temperatures obtained from the polarizing microscope and differential scanning calorimeter measurements agree well with the dielectric relaxation data.     

NMR relaxation study of molecular dynamics in columnar and smectic phases of a PAMAM liquid-crystalline co-dendrimer

We present the first results obtained by proton (¹H) nuclear magnetic relaxation studies of molecular dynamics in a supermolecular liquid-crystal dendrimer exhibiting columnar rectangular and smectic-A phases. The ¹H spin-lattice relaxation time (T₁) dispersions are interpreted using two relaxation mechanisms associated with collective motions and local molecular reorientations of the dendritic segments in the low- and high-frequency ranges, respectively. The T₁ values show a drop around 2.3 MHz that is attributed to a contribution coming from cross-relaxation between ¹H and nitrogen nuclear spins. In the high-frequency range the motions appear to be of similar nature in both mesophases and are ascribed to reorientations of dendritic segments (belonging to the core and/or to the mesogenic units) characterized by two correlation times. Notable differences in the dynamics between the columnar and layered phases are observed in the low-frequency range. Depending on the mesophase they are discussed in terms of elastic deformations of the columns and layer undulations. In this study we find that the dendritic core influences the dynamics of the mesogenic units both for local and collective motions. These results can be understood in terms of spatial constraints imposed by the dendritic architecture and by the supermolecular arrangement in the mesophases.     

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.     

Field-induced phase transitions and reversible field-induced inversion of chirality in tilted smectic phases of bent-core mesogens

Three homologous achiral five-ring bent-core mesogens are presented where 4-chlororesorcinol is the central core and the aromatic rings are linked by ester groups. These compounds form smectic phases with a tilted arrangement of the molecules (tilt angle ≈ 45^°). On cooling the isotropic liquid this phase adopts a fan-like texture which shows for two homologues at relatively high electric fields ( 25-35V μm^-1) an antiferroelectric electro-optical response based on the collective rotation of the molecules around their long axes. At lower temperature the application of a sufficiently high electric field leads to a continuous transition into a non-birefringent texture which exhibits randomly distributed domains of opposite handedness. These domains can be reversibly switched into a state of opposite chirality by reversal of the field polarity. This switching is bistable and shows a current response typical for a ferroelectric ground state. The possible mechanism of the field-induced phase transition, of the ferroelectric switching and of the field-induced inversion of the chirality is discussed on the base of XRD, ¹³C- and ¹H-NMR investigations, dielectric and electro-optical measurements.     

剪切作用下Cu(100)扭转晶界塑性行为研究

本文采用分子动力学方法研究了在剪切载荷作用下,Cu(100)扭转晶界对Cu柱屈服强度的影响.模拟结果发现,在加载过程中,低角度扭转晶界形成的位错网发生位错形核与扩展,位错之间的塞积作用提高了Cu柱的屈服强度;对于高角度扭转晶界,晶界发生滑动降低了Cu柱的屈服强度.同时发现,随着扭转角度的增加,Cu柱的屈服强度先增大,当扭转角度大于临界角度时,Cu柱的屈服应力逐渐减小.这表明剪切载荷作用下,两种不同的机理主导Cu柱的屈服,对于小于临界角度的扭转晶界,Cu柱的屈服由晶界位错形核和扩展机理主导,对于大于临界角度 关键词： 扭转晶界 分子动力学 位错形核 晶界滑移     

Macroscopic properties of smectic liquid crystals

We discuss the macroscopic behavior of smectic C_G liquid crystals. Smectic C_G is the most general tilted smectic phase that is fluid in the layers. It is characterized by global C₁ symmetry. Consequently, it is ferroelectric, pyroelectric and piezoelectric, opening up a number of possible applications for such a phase. As smectic C_G-phase has a macroscopic hand due to its structure, it is a natural candidate to explain the recent experimental observations of left and right-handed helices in a system composed of achiral molecules. We also discuss critically to what extent smectic C_G could be important for liquid crystalline phases formed by banana-shaped molecules. Phase transitions involving a smectic C_G phase and defects of its in-plane director are briefly discussed. Received: 25 March 1998 / Revised: 15 June 1998 / Accepted: 15 July 1998     

Correlation between the molecular chirality index and the spontaneous polarisation in series of smectic C* liquid crystals

A correlation between spontaneous polarisation and the chirality index of the constituent molecules, multiplied by the molecular transverse dipole, has been considered for five series of ferroelectric smectic C* liquid crystals. A good correlation has been found within each series, and it has been shown that the scaled chirality index may be used to estimate the spontaneous polarisation in a series of smectic C* mesogens with small systematic changes of the molecular structure. At the same time one cannot expect any significant correlation between the polarisation and the chirality index for smectic C* materials of sufficiently different structure because the spontaneous polarisation may be significantly effected by some details of the molecule's structure including the orientation of the transverse dipole with respect to the primary short molecular axis.     

Observation of edge dislocations in helical smectic liquid crystals

We report the observation of elementary edge dislocations in smectic liquid crystals possessing helical structure. The dislocations were observed in the entire temperature range of helical phases, including ferroelectric, ferrielectric and antiferroelectric phases. The mechanism for visualizing the dislocations is based on the phenomenon of selective reflection of circularly polarised light. The performed observations of dislocations deliver not only information on the mechanisms of defect creation in various chiral smectic phases, but also on the structure and properties of the investigated smectics, often inaccessible using standard methods.     

Laser manipulation of a smectic liquid-crystal droplet

The laser trapping of a smectic-A liquid-crystal micro-droplet was spatially traced during its transient into the trapped position. The lateral and angular orientation of the droplet were determined and followed in time during the axial descent of the micro-droplet into the stationary trapped position using the analysis of polarization changes of the light passed through the droplet with temporal resolution of a video refresh rate of 30 ms. The spatial resolution of 0.1-1μm has been achieved for typical laser trapping powers of 2-600 mW. The axial profile of a laser trapping force (an ellipticity of the focal spot) has been determined. The laser trapping mechanism of smectic micro-droplets is discussed in terms of minimization of a light-droplet interaction.     

Symmetries of the electrodynamic interactions between chiral molecules

A quantum electrodynamics calculation of the dynamic microscopic interactions between molecules beyond the electric dipole approximation is presented. The symmetry of the resulting terms is examined with respect to rotations, parity and index permutations. Their relative importance is also considered in the short-distance limit. A dominant term which exists only in chiral molecules and which involves the coupling of the anisotropic parts of the molecular optical activities is evidenced. Associated with the coupling of the anisotropic parts of the molecular polarisabilities which is usually invoked to account for the isotropic–nematic phase transition of liquid crystals, that term accounts for the possibility of the helical order which is observed in chiral nematics (cholesterics). Introducing in addition both the short-range correlations due to the exclusion principle driven repulsive forces and the thermally-induced effect of the static multipole interactions can explain the temperature dependence of the helical pitch. No assumption will be made on the shape of the molecules.     

Field-temperature phase diagrams in chiral tilted smectics,evidencing ferroelectric and ferrielectric phases

Usual ferroelectric compounds undergo a paraelectric-to-ferroelectric phase transition when the susceptibility of the electric polarization density changes its sign. The temperature is the only thermodynamic field that governs the phase transition. Chiral tilted smectics may also present an improper ferroelectricity when there is a tilt angle between the average long axis direction and the layer normal. The tilt angle is the order parameter of the phase transition which is governed by the temperature. Although the electric susceptibility remains positive, a polarization proportional to the tilt appears due to their linear coupling allowed by the chiral symmetry. Further complications come in when the chirality increases, as new phases are encountered with the same tilt inside the layers but a distribution of the azimuthal direction which is periodic with a unit cell of two (SmC(A)*, three (SmC(Fi1)*, four (SmC(Fi2)* or more (SmC(alpha)* layers. In most of these phases, the layer normal is a symmetry axis so there is no macroscopic polarization except for the SmC(Fi1)* in which the average long axis is tilted so the phase is ferrielectric. By studying a particular compound with only a SmC(Fi2)* and a SmC(alpha)* phase, we show that we recover the uniformly tilted ferroelectric SmC* when applying an electric field. We are thus led to build field-temperature phase diagrams for this class of compounds by combining different experimental techniques described here.     

Determination of the bulk rotational viscosity coefficient in a chiral smectic C* liquid crystal

The method of determination of the bulk values of the rotational viscosity coefficient of the smectic c-director in chiral smectic liquid crystals with a helical structure is described. The measurements were performed using optical detection in the small deformation limit. In contrast to the usual methods, the initial deformation of the helix (caused by strong surface interactions) was avoided by using homeotropic aligned thick samples. The coefficient was measured in 4-methylbutyloxy phenyl-4-octyloxy-benzoate (C8) in the presence of laminar flow. The critical temperature dependence of the measured coefficient was found. The relation between the measured coefficient and the smectic C order parameter is shown.