Colloidal inclusions in smectic films with spontaneous bend

Inclusions in free-standing smectic films are simple model systems for two-dimensional anisotropic dispersions. From theory and experiment, different topologies of elastic distortions of the embedding liquid crystal are known. Quadrupolar and different dipolar defect configurations in the vicinity of the inclusion are possible, and these configurations determine the type of interactions between the inclusions. The quadrupolar configuration is often energetically preferred. We show, however, that dipolar director configurations around inclusions can be energetically favourable over quadrupolar arrangements in chiral smectics, as a consequence of a spontaneous-bend term in the elastic-energy formulation. As the inclusion size influences the selection of the deformation types, the corresponding spontaneous-bend constant can be estimated for the strong anchoring limit if the c -director fields around inclusions of different diameters are taken into account.     

Defects in a TGBA phase: A theoretical approach

Following our experimental observations of disclination lines in freely suspended droplets and free-standing films (Yu.A. Nastishin et al., Eur. Phys. J. E 5 353 (2001)), topological defects of the twist grain boundary (TGBA) phase are considered according to two aspects: topological and energetical. There are two classes of line defects, disclinations (as in the cholesteric (N*) phase and the liquid vortices phase (NL*), relating to the directors tripod symmetries) and dispirations (relating to the translation-rotation symmetries); there are no topological point defects. Differences between N*, NL* and TGBA disclinations are physical, not topological. The absence of focal conic domains in the TGBA phase is an immediate consequence of the materialization of the helical axis (along the χ-director); the same feature, coupled to the trend to parallelism of the smectic layers, accounts for the predominance of λ-lines. Finally, the presence of defects akin to developable domains is explained in the frame of the leastcurvaturemodel, that requires the introduction of a third type of defects: the densitiesofedgedislocations of the smectic layers. Received 20 February 2002     

Water droplets in a spherically confined nematic solvent: A numerical investigation

Recently, it was observed that water droplets suspended in a nematic liquid crystal form linear chains [Poulin et al., Science 275, 1770 (1997)]. The chaining occurs, e.g., in a large nematic drop with homeotropic boundary conditions at all the surfaces. Between each pair of water droplets a point defect in the liquid crystalline order was found in accordance with topological constraints. This point defect causes a repulsion between the water droplets. In our numerical investigation we limit ourselves to a chain of two droplets. For such a complex geometry we use the method of finite elements to minimize the Frank free energy. We confirm an experimental observation that the distance d of the point defect from the surface of a water droplet scales with the radius r of the droplet like .When the water droplets are moved apart, we find that the point defect does not stay in the middle between the droplets, but rather forms a dipole with one of them. This confirms a theoretical model for the chaining. Analogies to a second order phase transition are drawn. We also find the dipole when one water droplet is suspended in a bipolar nematic drop with two boojums, i.e., surface defects at the outer boundary. Finally, we present a configuration where two droplets repel each other without a defect between them. Received 11 December 1998     

A chiral axial next nearest neighbour xy-model for antiferroelectric liquid crystals

We describe a chiral axial next nearest neighbour xy-model to account for the various subphases exhibited by antiferroelectric liquid crystals made of chiral rod-like molecules. The assumed form of the interlayer interactions is based on physical processes which are discussed. Using a discrete model, the predicted sequence of transitions is SmA-SmC-SmC-FI_H-FI_I-FI_L-SmC ^* A, where FI stands for a ferriphase, as seen in many compounds. The ferri and SmC phases are characterized by relatively large angles between the c-vectors of successive layers and occur only when the compounds have high optical purity. The calculated field induced structures exhibit a plateau of the apparent tilt angle at , where is the tilt angle of the molecules in the ferriphase. The conoscopic figures in the presence of a field and ellipsometric parameters in the absence of a field have also been generated, which agree extremely well with the experimental results. Recent anomalous X-ray scattering studies prove the xy-character of the configurations, though the commensurate structures that are found in the ferriphase require an extension of the model to include lock-in terms. Received 23 August 1999     

Colloidal dipolar interactions in 2D smectic-C films

We use a two-dimensional (2D) elastic free energy to calculate the effective interaction between two circular disks immersed in smectic-C films. For strong homeotropic anchoring, the distortion of the director field caused by the disks generates topological defects that induce an effective interaction between the disks. We use finite elements, with adaptive meshing, to minimize the 2D elastic free energy. The method is shown to be accurate and efficient for inhomogeneities on the length scales set by the disks and the defects, that differ by up to 3 orders of magnitude. We compute the effective interaction between two disk-defect pairs in a simple (linear) configuration. For large disk separations, D, the elastic free energy scales as ∼D ^-2, confirming the dipolar character of the long-range effective interaction. For small D the energy exhibits a pronounced minimum. The lowest energy corresponds to a symmetrical configuration of the disk-defect pairs, with the inner defect at the mid-point between the disks. The disks are separated by a distance that is twice the distance of the outer defect from the nearest disk. The latter is identical to the equilibrium distance of a defect nucleated by an isolated disk. Received 26 October 2001 and Received in final form 14 December 2001     

c-director relaxation around a vortex of strength +1 in free-standing smectic-C films

The relaxation of director fields in freely suspended smectic films is studied experimentally by means of polarizing microscopy, and analyzed by solving the torque balance equation under appropriate initial and boundary conditions. We consider in particular the role of anchoring conditions of the c-director at particles and defects in the film. The structure of regular relaxation patterns allows to determine the elastic anisotropy of smectic materials. The splay elastic constant can exceed the bend constant by a factor of two and more. A remarkable consequence of this anisotropy is the stick-slip-like relaxation around a central defect of topological strength s = + 1.     

Annihilation of nematic point defects: Pre-collision and post-collision evolution

The annihilation of the nematic hedgehog and anti-hedgehog within an infinite cylinder of radius R is studied. The semi-microscopic lattice-type model and Brownian molecular dynamics are used. We distinguish among the i) early pre-collision, ii) late pre-collision, iii) early post-collision, and iv) late post-collision stages. In the pre-collision stage our results agree qualitatively with the existing experimental observations and also continuum-type simulations. The core of each defect exhibits a ring-like structure, where the ring axis is set perpendicular to the cylinder symmetry axis. For ξ⁽⁰⁾_d/(2R) > 1 the interaction between defects is negligible, where ξ⁽⁰⁾_d describes the initial separation of defects. Consequently, the defects annihilate within the simulation time window for ξ⁽⁰⁾_d/(2R) < 1. For close enough defects their separation scales as ξ_d (t_c - t)^0.4±0.1, where t_c stands for the collision time. In elastically anisotropic medium the hedgehog is faster than the anti-hedgehog. In the early pre-collision stage the defects can be treated as point-like particles, possessing inherent core structure, that interact via the nematic director field. In the late pre-collision stage the cores reflect the interaction between defects. After the collision a charge-less ring structure is first formed. In the early post-collision stage the ring adopts an essentially untwisted circular structure of the radius ξ_r. In the late post-collision stage we observe two qualitatively different scenarios. For μ = ξ_r/R < μ_c ∼ 0.25 the ring collapses leading to the escaped radial equilibrium structure. For μ > μ_c the chargeless ring triggers the nucleation growth into the planar polar structure with line defects.     

Phases hexagonales colonnaires thermotrope et lyotrope : défauts observés par cryofracture et caractère anomal du thermotrope

Electron microscopy observations of replicas of freeze-fractured samples of two columnar hexagonal phases of different nature (a lyotropic one, the inverse AOT in water; a thermotropic one, ) yield very different results: most defects at microscopic scales are screw dislocations in the lyotropic phase, longitudinal edge dislocations in the thermotropic phase. A possible way to interpret these differences is as follows: in the lyotropic the Lamé coefficients and μ and the bend modulus K₃ would not display any anomaly compared to expected values; in the thermotropic the shear modulus μ would be ten times smaller than the compressibility modulus , while K₃ would still be comparable to (but larger than) the bend modulus of a small molecules liquid crystal. We present an elementary theoretical model of the latter case which could explain the anomalous measurements of K₃ and of the longitudinal compressibility (Ref. [#!ref10!#]) without contradicting more recent measurements of (Refs. [#!ref17!#,#!ref22!#]). Essentially, the hexagonal phase would be a phase with defects (longitudinal dislocations) akin to an hexatic phase but with some differences. Re?u : 26 mai 1997 / Révisé : 20 Janvier 1998 / Accepté : 27 avril 1998     

Orientational defects in freely suspended smectic <Emphasis Type="Italic">C</Emphasis> films

Linear orientational defects (2π and π walls) in freely suspended thin smectic C films exposed to a magnetic field were studied. The bend and splay elastic constants, as well as the orientational viscosity of a two-dimensional c-director field, were determined. It was established that a change in the polar and azimuthal angles of magnetic-field orientation in a sample cardinally transforms the wall structure. This is caused by the anisotropy of orientational elasticity of the c director.     

Features of the motion of a 180° domain boundary in a thin ferromagnetic film with defects

For a thin ferromagnetic film, the braking process of a 180° domain boundary in a field of randomly distributed point defects is studied using perturbation theory. It is established that, for low velocities, the motion of the boundary is nonsteady-state. It is shown that the critical velocity of steady-state motion depends substantially on film thickness and the defect concentration. Fiz. Tverd. Tela (St. Petersburg) 41, 1231–1235 (July 1999)     

Effect of the chiral chain length on structural and phase properties of ferroelectric liquid crystals

Studies of structural and phase properties obtained on several ferroelectric liquid crystalline materials with 2-alkoxypropionate group used as a chiral centre and without any lateral substitution are presented. In dependence on the chiral chain length these compounds exhibit the cholesteric N* phase, the ferroelectric smectic C* and a low-temperature SmX phase. Values of the spontaneous polarization and spontaneous tilt angle have been determined within the whole range of the SmC* phase. A low-temperature SmX phase has been identified as the orthogonal hexatic SmB* phase. The molecular parameters, namely the layer spacing in the SmC* and SmB* phases and the average intermolecular distances (D) between neighbouring parallel molecules in all investigated phases have been determined using the results of the X-ray diffraction obtained on non-oriented samples. The effect of the chiral chain length on mesomorphic, structural and physical properties of the studied ferroelectric liquid crystalline materials is discussed.     

Optical second-harmonic generation in ferroelectric chiral smectic polysiloxane

The second-order nonlinear optical properties of ferroelectric liquid crystalline polymer have been studied. Angular phase-matched Second-Harmonic Generation (SHG) is observed in the chiral smectic C (SmC*) phase of siloxane copolymer with chiral mesogen in the side chain. The effective nonlinear optical coefficient d_eff under the phase-matching condition is determined. The intense SHG is observed even in the crystalline phase by cooling down from the SmC* phase under the electric field. The effective coefficient of SHG in the crystalline phase is more than ten times larger than that of the phase-matched SHG in the SmC* phase. The enhancement of SHG in the crystalline phase is observed only in a homeotropically aligned cell and maintained even in the non-biased state for at least several days. The angular dependence of the SHG in the crystalline phase is confirmed.     

Soliton-like molecular deformations in a nematic liquid crystal film

We study the nature of molecular deformations in a nematic liquid crystal film with elastic energy under homeotropic boundary conditions. The deformation in terms of splay, twist and bend fields of the director axis is found to be governed by the completely integrable Davey-Stewartson-I (DS-I) equation in (2+1) dimensions. Using the line soliton and breather solutions of the DS-I equation, the director axis is constructed, the components of which exhibit damped spatial oscillations. However, the splay and bend fields of the director axis exhibit localized structures of deformation.     

Structure and elastic properties of a nematic liquid crystal: A theoretical treatment and molecular dynamics simulation

The Frank elasticity constants which describe splay (K ₁), twist (K ₂), and bend (K ₃) distortion modes are investigated for 4-n-pentyl-4'-cyanobiphenyl (5CB) in the nematic liquid crystal. The calculations rest on statistical-mechanical approaches where the absolute values of K _i (i=1,2,3) are dependent on the direct correlation function (DCF) of the corresponding nematic state. The DCF was determined using the pair correlation function by solving the Ornstein-Zernike equation. The pair correlation function, in turn, was obtained from molecular dynamics (MD) trajectory. Three different approaches for calculations of the elasticity constants were employed based on different level of approximation about the orientational order and molecular correlations. The best agreement with experimental values of elasticity constants was obtained in a model where the full orientational distribution function was used. In addition we have investigated the approximation about spherical distribution of the intermolecular vectors in the nematic phase, often used in derivation of various mean-field theories and employed here for the construction of the DCF. We found that this assumption is not strictly valid, in particular a strong deviation from the isotropic distribution is observed for short intermolecular distances. Received 22 March 2000 and Received in final form 9 June 2000     

Frustration between syn- and anticlinicity in mixtures of chiral and non-chiral tilted smectic-C-type liquid crystals

We study the effects of mixing ferroelectric and antiferroelectric liquid-crystal compounds (FLCs and AFLCs) when the former are strictly synclinic and the latter strictly anticlinic, i.e. one mixture component exhibits only SmC* and the other only SmC a* as tilted phase. Three different paths between syn- and anticlinicity were detected: transition directly between SmC* and SmC a*, transition via the SmC_β* and SmC_γ* subphases, or by “escaping” the clinicity frustration by reducing the tilt to zero, i.e. the SmA* phase is extended downwards in temperature, separating SmC* from SmC a* in the phase diagram. The most common path is the one via the subphases, demonstrating that these phases appear as a result of frustration between syn- and anticlinic and, consequently, between syn- and antipolar order. For assessing the role of chirality, we also replaced the FLC with non-chiral synclinics. With one of the AFLCs, the route via supbhases was detected even in this case, suggesting that chirality --although necessary-- does not have quite the importance that has previously been attributed to the appearance of the subphases. The path chosen in the mixture study seemed to be determined mainly by the synclinic component, the subphase induction occurring only when the SmA*-SmC* transition was second order.     

EPR Investigations on Molecular Orientation of Paramagnetic Liquid Crystals in a Surface-Stabilized Liquid Crystal Cell: Studies on a Smectic C or Chiral Smectic C Phase

By electron paramagnetic resonance spectroscopy we investigated the molecular orientation in a surface-stabilized liquid crystal (LC) cell, which includes a racemic (±) or an enantiomerically enriched (S,S) paramagnetic LC, (2S,5S)-2,5-dimethyl-2-tridecyloxyphenyl-5-[4-(4-tridecyloxy-benzenecarbonyloxy)phenyl]pyrrolidine-1-oxy (2), whose spin source is fixed inside the rigid core. For both the smectic C (SmC) phase of (±)-2 and the chiral smectic C (SmC^*) phase of (S,S)-2 in a surface-stabilized LC cell (antiparallel configuration, thickness of 4 μm), the profile of the observed g-value as a function of the angle between the applied magnetic field and the cell plane could be explained by the orientation model, where, with some disordering, the molecules align uniformly with the direction which tilts from the normal line of the smectic layer being orthogonal to the rubbing direction on the cell surface. We divided the effect from the disordering into two parts, one of which is concerning the direction of the molecular long axis and the other is concerning the rotation around the molecular long axis. As a result of the analysis, the SmC^* phase gave quite lower ordering concerning the direction of the molecular long axis and a little lower ordering concerning the rotation around the molecular long axis than the SmC phase at the same temperature (80 °C). The obtained lower ordering in the SmC^* phase is probably due to the chirality that would result in the formation of a helical superstructure in a bulky state. Authors' address: Yohei Noda, Laboratory of Electron Spin Chemistry, Department of Chemistry, Graduate School of Science, Kyoto University, 606-8502 Kyoto, Japan     

Identification of a TGBA liquid crystal phase via its defects

We have shown that cholesteryl nonanoate, a thermotropic compound which is well known to exhibit pretransitional effects at the smectic A (SmA) cholesteric (N*) transition (W.L. McMillan, Phys. Rev. A 4, 1238 (1971); 6, 936 (1972)), has in fact a TGBA phase in between. Our arguments rely on the observation of new TGBA defects, either in Robinson spherulites cooled from the N* phase or in free-standing films. The same new defects can be obtained in a well-documented TGBA phase of a tolane compound. We analyze qualitatively the TGBA defects in both geometries, in particular their relation to the disclination radius of the N* Robinson spherulites. Received 12 February 2001     

Director field configurations around a spherical particle in a nematic liquid crystal

We study the director field around a spherical particle immersed in a uniformly aligned nematic liquid crystal and assume that the molecules prefer a homeotropic orientation at the surface of the particle. Three structures are possible: a dipole, a Saturn-ring, and a surface-ring configuration, which we investigate by numerically minimizing the Frank free energy supplemented by a magnetic-field and a surface term. In the dipole configuration, which is the absolutely stable structure for micron-size particles and sufficiently strong surface anchoring, a twist transition is found and analyzed. We show that a transition from the dipole to the Saturn ring configuration is induced by either decreasing the particle size or by applying a magnetic field. The effect of metastability and the occurrence of hysteresis in connection with a magnetic field are discussed. The surface-ring configuration appears when the surface-anchoring strength W is reduced. It is also favored by a large saddle-splay constant K₂₄. A comparison with recent experiments [#!itapdb:Poulin1997!#,#!itapdb:Poulin1998!#] gives a lower bound for W, i.e., for the interface of water and pentylcyanobiphenyl (5CB) in the presence of the surfactant sodium dodecyl sulfate. Received 2 November 1998