Rupture and recoil of bent-core liquid crystal filaments.

The recoil process of free-standing liquid crystal filaments is investigated experimentally and theoretically. We focus on two aspects, the contraction speed of the filament and a spontaneously formed undulation instability. At the moment of rupture, the filaments buckle similarly to the classical Euler buckling of elastic rods. The tip velocity decays with decreasing filament length. The wavelength of buckling affinely decreases with the retracting filament tip. The energy gain related to the decrease of the total length and surface area of the filaments is mainly dissipated by layer rearrangements during thickening of the fibre. A flow back into the meniscus is relevant only in the final stage of the recoil process. We introduce a model for the quantitative description of the filament retraction speed. The dynamics of this recoil behaviour may find relevance as a model for biology-related filaments.

Direct observation of smectic layers in thermotropic liquid crystals.

We demonstrate subnanometer resolution cryo-TEM imaging of smectic layers in the smectic and nematic phases of two bent-core liquid crystals. Our results show perfect periodicity over several hundred layers in the smectic phase and also provide the first direct evidence of smectic clusters on length scales of 30-50 nm in a nematic liquid crystal. The results are corroborated with small angle x-ray scattering measurements. The observation of smectic clusters in the nematic phase is of special interest in bent-core liquid crystals, where the smectic clusters are stable over wide temperature ranges, in contrast to the well-known pretransitional "cybotactic" clusters that appear only in the vicinity of a bulk smectic phase. The means to characterize and manipulate this nanoscale molecular order could open up completely new liquid crystal-based technologies.

Characterization of a chiral phase in an achiral bent-core liquid crystal by polarization studies of resonant x-ray forbidden reflections.

The chiral antiferroelectric structure of an achiral bent-core liquid crystal is characterized by resonant x-ray scattering at chlorine K edge. The "forbidden" reflections resulting from the glide or screw symmetry elements are restored by the anisotropy of the tensor structure factor, which we calculate for two possible structural models. A careful analysis of the polarization states of the restored "forbidden" reflections enables an unambiguous identification of a chiral structure (i.e., the so-called anticlinic, antiferroelectric smectic-C or Sm-C(A)P(A)) coexisting with the achiral synclinic antiferroelectric smectic-C or Sm-C(S)P(A). The method proves to be quite powerful as it identifies the chiral structure within coexisting phases despite an imperfect orientation of the sample. The volume fraction of the chiral phase and the distribution of alignment are extracted from the data.

Bundles of fluid fibers formed by bent-core molecules.

The internal structures, stability, and elastic properties of free-standing filament bundles of bent-core smectic liquid crystals are studied using polarizing microscopy, scanning electron microscopy, and a customized cantilever containing, temperature controlled heat stage for force measurements. We find that in bundles, the individual filaments fuse together to form semiseparable filaments with radii approximately two and three times larger than the individual fibers. We also find that the effective surface tension of wide bundles is about 10% smaller than a single filament. Finally, we describe the metastable coexistences of single fibers within the bundles that lead to bending of the bundles. All of these observations were explained with simple macroscopic models.

Multiple electroconvection scenarios in a bent-core nematic liquid crystal.

We report on the anisotropic electrohydrodynamic states formed over a wide temperature range (∼45 °C) in a planarly aligned bent-core nematic liquid crystal driven by fields of frequency in the range 0.1 Hz-1 MHz. Three different primary bifurcation scenarios are generated in the voltage-frequency (V-f) plane, depending on the temperature T. These, under increasing T, are characterized by the pattern sequences (i) in-plane longitudinal rolls (ILR)→in-plane normal rolls 1 (INR1), (ii) Williams rolls (WR)→ILR→INR1, and (iii) WR→INR2→INR1. Temperature-induced ILR→INR2 transition, the first example of its kind, points to elastic anisotropy as possibly the determining factor in wave vector selection. In the ILR and INR states, at threshold, the director modulations are predominantly azimuthal, and the streamlines, mainly normal to the wave vector, lie in the sample plane. Well above threshold, growing director deviations lead to narrow disclination loops that evolve in regular arrays, with their area density being exponential in voltage. The defects drift in a coordinated manner along the flow lines with a speed that scales nonlinearly with voltage; they mediate in the eventual occurrence of turbulence. The current theories of anisotropic convection based on static electrical parameters fail to account for the observed high-frequency instabilities. The study includes (i) a quantitative characterization of the critical parameter functions V(c)(f), V(c)(T), q(c)(f), and q(c)(T), with q(c) denoting the critical pattern wave number, and (ii) measurement of electrical and elastic parameters of relevance to electroconvection; the latter show anomalous features supporting the cluster hypothesis.

Optical waveguiding in bent-core liquid-crystal filaments.

We demonstrate optical waveguiding in recently discovered free-standing bent-core liquid-crystal filaments. The bent-core liquid-crystal molecules in air self-assemble into a cylindrical geometry that is "solidlike" along the radial direction of the filament and liquid in the axial direction of the filament. These filaments are unique not only because they are fluids, but also because they are anisotropic. For this reason, their waveguiding properties not predictable need to be characterized. The light power transmitted through the filament was found to be independent of temperature from 180 degrees C to near room temperature. Initial defects of newly pulled filaments were found to self-anneal, thus leaving defect-free fibers, where light scattering was found to be insignificant. The absorbance was found to be strongly wavelength dependent in the visible regime and relatively small in the infrared range. A self-assembled optical waveguide with self-annealing fluid properties may have promising applications in optical communications or in optical microchips.

Multistage polar switching in bent-core mesogens.

We report a novel type of electro-optical switching in a tilted smectic phase of bent-shaped mesogens. The switching consists of a continuous stage and two bistable transitions. Detailed optical and electro-optical measurements using high-speed imaging are given and possible interpretations of the experimental results are discussed.

Polarization splay as the origin of modulation in the B1 and B7 smectic phases of bent-core molecules.

We report a generalized scenario for the formation of modulated smectic phases of bent-core molecules based on locally ferroelectric layering and spontaneous splay of the polarization. Twelve phases are proposed, distinguished by neighboring splay stripes with either syn- or antiorder of the polarization and undulation slope, in addition to layer continuity versus layer discontinuity at the intervening defects. We outline the experimental techniques necessary to differentiate among the phases and interpret previous results in the present context, using high resolution x-ray scattering diffraction and block and undulation models of the layer organization to distinguish among the three 2D lattice types which emerge.

Electro-optic characterization of a nematic phase formed by bent core mesogens.

The purpose of this paper is the demonstration that bent core nematic phases behave quantitatively and qualitatively very different from ordinary calamitic nematics in their electro-optical characteristics. We present measurements of the elastic properties from the analysis of Brochard-Leger walls that are formed during the splay Fréedericksz transition in sandwich cells. These walls possess an unusually large shape anisotropy as compared to similar structures in calamitic nematics. The wall shapes can be explained when one assumes that the bend elastic constant K(33) is one order of magnitude larger than the twist constant K(22) of the material, supposing that flexoelectricity in the description of the elastic deformations can be neglected. Further we report periodic structures above the splay Fréedericksz transition with a wave vector perpendicular to the director easy axis. They represent either a static instability or an unconventional type of electrically driven convection.

Field-induced texture transitions in a bent-core nematic liquid crystal.

It is demonstrated in electro-optic experiments that an external electric field of the order of 10;{5} V/m induces persisting texture transitions in a nematic phase formed by bent-core mesogens. The field-induced metastable state is identified by its optical and electric properties. After the field is switched off, the original and induced states can coexist in domains for about one hour in planar sandwich cells. During this time, the induced domains gradually shrink but they can be stabilized in moderate electric fields. The occurrence of similar domains in homeotropic cells suggests that the transition into a metastable biaxial state is observed. In the field-free planar ground state, the formation of inversion walls is observed inside the metastable domains.

Electric-field-induced chirality flipping in smectic liquid crystals: the role of anisotropic viscosity.

We demonstrate the homogeneous and permanent reversal of the chirality of a condensed phase by an applied electric field. Tilted chiral smectic layers exhibit a coupled polarization density and molecular orientation fields which reorient about the layer normal as couple of fixed handedness in response to small applied electric fields. Experiments on some bent-core smectics show that above a threshold field the induced rotation can occur instead about the molecular long axis and that, as a result, the handedness of the phase can be flipped. The effect is quantitatively described by a nonequilibrium dissipative model of chiral smectic dynamics with anisotropic rotational viscosities.

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 approximately 45 degrees). On cooling the isotropic liquid this phase adopts a fan-like texture which shows for two homologues at relatively high electric fields ( 25-35 V microm(-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.

Optically isotropic liquid-crystal phase of bent-core molecules with polar nanostructure.

We found that the optically isotropic (I(M)) mesophase observed recently below the nematic phase of the bent-core liquid crystal 4-chlororesorcinol bis[4-(4-n-dodecyloxybenzoyloxy)benzoate] shows ferroelectric-type switching. Polarizing microscopic, electric current, dielectric, and dynamic light scattering studies lead us to propose that the I(M) phase is composed of interconnected orthoconic racemic smectic (Sm-Ca P(F)) nanodomains with random layer orientations. Near the nematic phase, where the polarization can be saturated by electric fields, the system responds in a fashion analogous to the granular structure of a magnetic spin glass--in particular, we observed that the relaxation back to the nonpoled structure follows a similar, inverse logarithmic rule.

Polarization-modulated smectic liquid crystal phases.

Any polar-ordered material with a spatially uniform polarization field is internally frustrated: The symmetry-required local preference for polarization is to be nonuniform, i.e., to be locally bouquet-like or "splayed." However, it is impossible to achieve splay of a preferred sign everywhere in space unless appropriate defects are introduced into the field. Typically, in materials like ferroelectric crystals or liquid crystals, such defects are not thermally stable, so that the local preference is globally frustrated and the polarization field remains uniform. Here, we report a class of fluid polar smectic liquid crystals in which local splay prevails in the form of periodic supermolecular-scale polarization modulation stripes coupled to layer undulation waves. The polar domains are locally chiral, and organized into patterns of alternating handedness and polarity. The fluid-layer undulations enable an extraordinary menagerie of filament and planar structures that identify such phases.

Field-induced switching between states of opposite chirality in a liquid-crystalline phase.

A tilted smectic phase of a new achiral banana-shaped mesogen is presented. It possesses liquidlike order within the layers and appears with a fan-shaped texture. At sufficiently high electric fields, this texture can be transformed into a texture that displays a complete extinction between crossed polarizers and it forms randomly distributed chiral domains. Above a threshold these domains can be reversibly switched into a state of opposite handedness.

Experimental evidence for Sm-CG-->Sm-CP polymorphism in fluorinated bent-shaped mesogens.

We report the experimental results on pure fluorinated bent-shaped mesogens showing very unusual textures and electro-optical behavior. In the view of recent publications such behavior can be explained by triclinic symmetry of the mesophase (Sm-C(G)) formed by these compounds. Based on the results of the x-ray diffraction and electro-optical investigations, we give evidence for the Sm-C(G) -->Sm-CP polymorphism.

Optical studies on free-standing films of an achiral smectic liquid crystal.

Employing null transmission ellipsometry and depolarized reflected light microscopy, we have studied two smectic phases, Sm-C1 and Sm-C2, of one achiral mesogen. Our results show that Sm-C1 and Sm-C2 are the synclinic Sm-C and anticlinic Sm-C(A) phases, respectively. We find no evidence to support recent claims that the Sm-C1 is chiral and ferroelectric [R. Stannarius et al., Phys. Rev. Lett. 90, 025502 (2003)].

Observation of unusual surface ordering in a uniaxial Sm-A phase formed by a highly biaxial compound.

We have studied one banana-shaped compound using null-transmission ellipsometry. By studying free-standing films of various thicknesses we confirm that this compound exhibits the Sm-A phase. This is the first banana-shaped compound with a relatively small bend angle (approximately 140 degrees) in which a uniaxial phase has been observed. At the lower temperature end of the Sm-A phase we observe unusual ordering at the surface of the film.

Experimental evidence for an achiral orthogonal biaxial smectic phase without in-plane order exhibiting antiferroelectric switching behavior.

We report unambiguous experimental evidence for an achiral orthogonal biaxial smectic-A phase which exhibits antiferroelectric switching behavior. The evidence is based on x-ray-diffraction measurements, texture observation, and the results of dielectric and electro-optical measurements.

Detailed optical studies of several banana-shaped compounds in liquid crystal B2 phase.

Null-transmission ellipsometry has been performed on free-standing films of one compound in the liquid crystal B2 phase. We have studied films of thickness from 1 to 121 layers. One of the compounds used has an unusually wide 59 K window for the B2 phase. The tilt angle was investigated as a function of temperature and found to be constant over this temperature range to within our resolution of 1 degrees. The one-layer films studied exhibit the same structure as the thicker films, and have helped us to refine the optical model for the B2 phase. For thin films we find that modeling a single smectic layer as two uniaxial layers is a better description of the data than a single biaxial layer, but that for thick films the model used does not effect the simulated result appreciably. Preliminary results also find that the surface layers are less tilted than the interior layers, in contrast to rodlike liquid crystals, which show an enhanced surface tilt.