Thermotropic biaxial nematic phase in liquid crystalline organo-siloxane tetrapodes

Infrared absorbance measurements have been carried out on two liquid crystalline organo-siloxane tetrapodes. Results unambiguously show the existence of a biaxial nematic phase below a uniaxial nematic phase. The three components of IR absorbance are used to calculate the various order parameters. On cooling, a weak first-order transition from isotropic to nematic is observed, followed by a second-order phase transition to biaxial nematic where the biaxiality parameters are found to be significantly large. Results are supported by observations from conoscopy and texture. Temperature dependences of the order parameters are well explained by the mean-field model for a biaxial phase.     

Thermotropic biaxial nematic liquid crystals

We have synthesized liquid crystal (LC) mesogens based on a nonlinear oxadiazole unit that exhibit nematic phases near 200 degrees C. Polarized microscopy and conoscopy indicate that these LCs are biaxial nematics. Unambiguous and quantitative evidence for biaxiality is achieved using 2H NMR spectroscopy. "2D powder" spectra, obtained by rotating 2H-labeled samples about an axis perpendicular to the magnetic field at approximately 200 Hz, yield phase biaxiality parameters of approximately 0.1 when coupled with rigorous and proven simulations.     

Polydispersity stabilizes biaxial nematic liquid crystals

Inspired by the observations of a remarkably stable biaxial nematic phase [van?den?Pol et?al., Phys. Rev. Lett. 103, 258301 (2009)], we investigate the effect of size polydispersity on the phase behavior of a suspension of boardlike particles. By means of Onsager theory within the restricted orientation (Zwanzig) model we show that polydispersity induces a novel topology in the phase diagram, with two Landau tetracritical points in between which oblate uniaxial nematic order is favored over the expected prolate order. Additionally, this phenomenon causes the opening of a huge stable biaxiality regime in between uniaxial nematic and smectic states.     

Emergent biaxiality in nematic microflows illuminated by a laser beam

Anisotropic fluids (e.g. liquid crystals) offer a remarkable promise as optofluidic materials owing to the directional, tunable, and coupled interactions between the material, flow, and the optical fields. Here we present a comprehensive in silico treatment of this anisotropic interaction by performing nonequilibrium molecular dynamics simulations. We quantify the response of a nematic liquid crystal (NLC) undergoing a Poiseuille flow in the Stokes regime, while being illuminated by a laser beam incident perpendicular to the flow direction. We adopt a minimalistic model to capture the interactions, accounting for two features: first, the laser heats up the NLC locally; and second, the laser polarises the NLC and exerts an optical torque that tends to reorient molecules of the nematic phase. Because of this reorientation the liquid crystal exhibits small regions of biaxiality, where the nematic director is one symmetry axis and the axis of rotation for the reorientation of the molecules is the other one. We find that the relative strength of the viscous and the optical torques mediates the flow-induced response of the biaxial regions, thereby tuning the emergence, shape and location of the regions of enhanced biaxiality. The mechanistic framework presented here promises experimentally tractable routes toward novel optofluidic applications based on material-flow-light interactions.     

A biaxial nematic liquid crystal composed of matchbox-symmetric molecules

By means of Monte Carlo simulations in the isothermal-isobaric ensemble, we investigate the structure and phase behaviour of a thermotropic liquid crystal composed of matchbox-symmetric (or board-like) molecules. Besides the isotropic phase the liquid crystal exhibits also uniaxial and biaxial nematic phases. The interaction potential is derived through an expansion in terms of Stone's rotational invariants [A. J. Stone, Mol. Phys. 78, 241–256 (1978).] that can be reexpressed in terms of Cartesian tensors. This latter formulation is particularly well suited for computer simulations. We analyse the orientation distribution function which allows us to distinguish between intrinsic and extrinsic biaxiality. In addition, we study the orientation-dependent correlation functions. In the limit of large intermolecular separations, the value of the orientation correlation function corresponds to the uniaxial and biaxial order parameters which are coupled in a complex fashion.     

The formation of biaxial nematic phases in binary mixtures of thermotropic liquid-crystals composed of uniaxial molecules

ABSTRACT

Monte Carlo simulations in the isothermal-isobaric ensemble are used to investigate the formation of an ordered, biaxial nematic phase in a binary mixture of thermotropic liquid crystals. The orientational dependence of the interaction between molecules of each pure component is the same as in the well-known Maier-Saupe model; each pure component of the mixture is therefore capable of forming a uniaxial nematic phase. For the interaction between molecules of different components, we use the same Maier-Saupe model but change the sign of the coupling constant. As a consequence a T-shaped arrangement of these molecules is energetically favoured. The formation of the biaxial phase occurs in two steps. At higher temperatures T, one of the components forms a uniaxial nematic phase whereas the other is in a quasi two-dimensional restricted isotropic liquid state. We develop a simple theoretical model to understand the high degree of (ostensible) nematic order in the latter. At lower T, the second component becomes nematic and then the entire mixture of the two compounds has biaxial symmetry. The biaxial nematic phase does not demix into domains rich in molecules of one or the other species.     

Biaxial nematic phase in bent-core thermotropic mesogens

A biaxial nematic phase had been predicted with D(2h) symmetry, wherein the mesogen's long and short transverse axes are simultaneously aligned along the two orthogonal, primary and secondary directors, n and m, respectively. The unique low-angle x-ray diffraction patterns in the nematic phases exhibited by three rigid bent-core mesogens clearly reveal their biaxiality. The results of x-ray diffraction can be readily reproduced by ab initio calculations that explicitly include the bent-core shape in the form factor and assume short-range positional correlations.     

Detection of phase biaxiality in liquid crystals by use of the quadrupole shift in 131Xe NMR spectra

An experimental method to unambiguously distinguish between uniaxial and biaxial liquid crystal phases is introduced. The method is based on the second order quadrupole shift (SOQS) observable in 131Xe NMR spectra of xenon dissolved in liquid crystals. It is shown that besides revealing the biaxiality, the 131Xe SOQS offers a novel method to determine the tilt angle in smectic C phases. As an example, the 131Xe SOQS in a ferroelectric liquid crystal is reported. It yields up a biaxial phase in between isotropic and smectic C phases.     

Fluctuations of orientational order in a uniaxial nematic liquid crystal with biaxial molecules and its response to an external field

Homogeneous thermal fluctuations of the orientational order parameters S and G of biaxial molecules in a uniaxial nematic liquid crystal are investigated in the framework of the molecular-statistical theory. It is demonstrated that the molecular biaxiality significantly affects the order parameters S and G, their temperature dependences in the nematic phase, the amplitude and the temperature dependence of the order parameter fluctuations in the nematic and isotropic phases, and the character of the transition from the nematic phase to the isotropic liquid phase. It is established that the fluctuations of the parameters S and G in the nematic phase are related to the temperature dependences of S and G and the susceptibilities χ_S and χ_G of the nematic liquid crystal to external fields, which leads to a change in the parameters S and G at a fixed director orientation. Explanations are offered for the known experimental data on the orientational ordering of biaxial molecules under the action of external fields in the isotropic phase of nematic liquid crystals.     

分子双轴性与向列型液晶在各向同性相的最低过冷温度

在分子场近似下,研究分子双轴性对向列型液晶在各向同性相最低过冷温度T^*的影响.理论结果表明,通过考虑分子双轴性,各向同性相最低过冷温度T^*与向列相—各向同性相相变温度T_c的比值向实验值靠近.当分子双轴性参数δ取到0.3时,T^*/T_c达到0.9817,已很接近0.99的实验值. 关键词：     

双轴性向列相液晶的相变理论

假设一双轴性向列相液晶分子简单相互作用模型，利用平均场理论，得到从各向同性相至单轴向列相、单轴向列相至双轴向列相的相变. 结果表明，在一定温度范围内，分子形状的非轴对称性可导致系统双轴向列相的产生. 在核磁共振实验中，导出双轴向列相序参数与谱线分裂频率间的一般关系，并讨论序参数测量性的可能性. 关键词： 向列相液晶 相变     

Influence of dipole-dipole correlations on the stability of the biaxial nematic phase in the model bent-core liquid crystal

A molecular theory of biaxial nematic ordering in the system of bent-core molecules has been developed in the two-particle cluster approximation which enables one to take into account short-range polar correlations determined by both electrostatic dipole-dipole interaction and polar molecular shape. All orientational order parameters and short-range correlation functions are calculated numerically as functions of temperature in the uniaxial and in the biaxial nematic phases, and the results are compared with the ones obtained in the mean-field approximation and in the cluster approximation but without taking into consideration the dipole-dipole interaction. It is shown that short-range polar correlations and, in particular, the dipole-dipole correlations dramatically increase the temperature of the transition into the biaxial nematic phase and enhancing its stability range. The results are also very sensitive to the value of the opening angle of a model bent-core molecule.     

Deuterium NMR investigation of the biaxial nematic phase in an organosiloxane tetrapode

Deuterium NMR is used to examine the molecular order exhibited by an organosiloxane tetrapode giving the first experimental evidence, using a bulk sample, for the existence of a biaxial nematic phase in this type of compounds. The temperature dependence of the averaged quadrupolar coupling constant and asymmetry parameter was determined in the compound's nematic phase. Two distinct regimes could be identified, one with a vanishing asymmetry parameter corresponding to a uniaxial nematic phase and another with a significant temperature dependent asymmetry parameter, corresponding to a biaxial nematic phase. The high values obtained for the asymmetry parameter at the lower end of the nematic range are well above experimental error and constitute a definite proof of the biaxial nature of the nematic phase exhibited by the studied compound for those temperatures.     

弹性形变对丝状相液晶相变的影响

应用Saupe形式的弹性自由能,研究了简单的扭曲,展曲和弯曲形变对相变的影响.结果表明,弹性形变可以产生从各向同性相至双轴丝状相的一级相变,对螺状相液晶,当系统手征性增加并超过某一临界值时,一级相变可过渡到二级相变. 关键词：     

The effects of molecular shape and quadrupole moment on tilted smectic phase formation

Results are presented from constant NPT Monte Carlo simulations of two systems based on the biaxial internally rotated Gay-Berne (IRGB) potential. First, the effect of increasing molecular elongation is considered, and it is shown that a change in aspect ratio from 3:1 to 4:1 leads to nematic and tilted smectic J phases being replaced by smectic A and tilted smectic G phases, respectively. Second, the effect of a longitudinal electric quadrupole on the phase behaviour of the IRGB model is examined. The presence of a moderate quadrupole moment results in the smectic G phase being replaced by a smectic J; the onset pressure of the smectic J increases monotonically as the quadrupole moment is increased, although the integrity of the tilted layers improves. In addition, the region of smectic A stability is found to persist for moderate quadrupole moment values. For the largest quadrupole moment considered, domains comprising poorly defined, tilted layers are formed but fail to develop into coherent smectic structures. This observation is ascribed to the competition between the unique tilt direction favoured by the biaxial IRGB potential and the random tilt direction of the uniaxial quadrupole-quadrupole interactions.     

A biaxial nematic gel phase in aqueous vanadium pentoxide suspensions

Aqueous suspensions of V₂O₅ ribbons are one of the very few examples of mineral liquid crystals. In the concentrated regime, we show that these ribbons organize in a biaxial nematic gel phase. A Couette shear cell was used to produce a well oriented sample for in situ synchrotron X-ray scattering studies. We observed two perpendicular anisotropic sections of reciprocal space, which proves the biaxial symmetry of the nematic order. The thermodynamic and flow properties of the biaxial nematic are well described by hard-core theories. We suggest the use of a shear geometry to produce and investigate single domains of other biaxial nematics, reported but still questioned in the literature. Received 26 May 1999     

Physical properties of aqueous suspensions of goethite ($\alpha$-FeOOH) nanorods

At volume fractions larger than 8.5%, aqueous suspensions of lath-like goethite (alpha-FeOOH) nanorods form a lyotropic nematic phase. In this article, we first discuss the nematic ordering within statistical-physics models of the isotropic/nematic phase transition. We then describe the influence of a magnetic field on the nematic phase. Because the nanorods bear permanent magnetic moments, the nematic suspensions have dipolar order and very low Frederiks thresholds. Moreover, the nematic phase aligns parallel to a small magnetic field but realigns perpendicular to a high field because of a competition between the permanent moments of the nanorods and their negative anisotropy of magnetic susceptibility. This magneto-optical study of the nematic phase is completely consistent with that of the isotropic phase of the same suspensions published in Part I (this issue, p. 291). Besides, we demonstrate the field-induced biaxiality of a nematic single domain aligned perpendicular to the field. We also describe here preliminary experiments where an a.c. electric field is applied to the nematic phase. Both field amplitude and frequency were found to control the alignment direction and homeotropic-to-planar alignment transitions were observed. From this data, simple models were used to estimate some physical constants of the nematic phase.     

Entropy-driven aggregation of adhesion sites of supported membranes

A large number of interesting phenomena related to the insertion of colloidal particles in liquid crystals (LC) have recently been reported. Here, we investigate effects caused by the addition of spherically shaped ferroelectric nanoparticles to a nematic liquid crystal. Using molecular dynamics (MD) simulations, the density of LC molecules, the orientational order parameter, and the polar and azimuthal angle profiles are calculated as functions of the distance to the center of the immersed nanoparticle for different temperatures of the system. We observe that the assembly of ferroelectric nanoparticles enhances the nematic order in the LC medium changing many properties of its host above the nematic-isotropic transition temperature T ^* _NI .     

The elusive thermotropic biaxial nematic phase in rigid bent-core molecules

The biaxial nematic liquid crystalline phase was predicted several decades ago. Several vigorous attempts to find it in various systems resulted in mis-identifications. The results of X-ray diffraction and optical texture studies of the phases exhibited by rigid bent-core molecules derived from 2,5-bis-(p-hydroxyphenyl)-l,3,4-oxadiazole reveal that the biaxial nematic phase is formed by three compounds of this type. X-ray diffraction studies reveal that the nematic phase of these compounds has the achiral symmetry D_2h, in which the overall long axes of the molecules are oriented parallel to each other to define the major axis of the biaxial phase. The apex of the bent-cores defines the minor axis of this phase along which the planes containing the bent-cores of neighboring molecules are oriented parallel to each other.