Laser-driven microflow-induced bistable orientation of a nematic liquid crystal in perfluoropolymer-treated unrubbed cells.

We demonstrate laser-driven microflow-induced orientational change (homeotropic to planar) in a dye-doped nematic liquid crystal. The homeotropic to planar director alignment is achieved in unrubbed cells in the thermal hysteresis range of a discontinuous anchoring reorientation transition due to the local heating by light absorption in dye-doped sample. Various bistable patterns were recorded in the cell by a programmable laser tweezers. The width of the patterns depend on the scanning speed of the tightly focussed laser beam and the minimum width obtained is approximately equal to 0.57µm which is about 35 times smaller than the earlier report in the rubbed cells. We show that the motion of the microbeam spot causes local flow as a result the liquid crystal director is aligned along that direction.

Viscoelasticity of ambient-temperature nematic binary mixtures of bent-core and rodlike molecules.

We report measurements of the temperature variations of physical parameters in ambient-temperature nematic liquid crystal mixtures of bent-core (BC) and rodlike molecules (5CB): birefringence Δn; static dielectric constants ε(||) and ε(⊥); splay K(11) and bend K(33) elastic constants; rotational viscosity γ(1); and diffusion coefficients D(||) and D(⊥) of a microsphere. Both Δn and ε(||) decreases rapidly with increasing BC concentration, whereas ε(⊥) remains almost constant. At a shifted temperature (e.g., T-T(NI)=-10 °C), K(11) increases by ~50% and K(33) decreases by ~80% compared to pure 5CB when the BC concentration is increased to ~43 mol % in the mixture. Viscosities parallel and perpendicular to the director, η(||), η(⊥), which are nearly equal to the Miesowicz viscosities η(2) and η(3), respectively, were obtained by D(||) and D(⊥) using the Stokes-Einstein relation. Both the viscosities at room temperature increase by 60 and 50 times, respectively, whereas γ(1) increases by 180 times (at ~43 mol %) compared to the corresponding values of pure 5CB. The stiffening of K(11) and exorbitantly large enhancement in all the viscosities at a higher mol % of BC indicate that the viscoelastic properties are highly impacted by the presence of smectic clusters of BC molecules that results from the restricted free rotation of the molecules along the bow axis in the nematic phase. A possible attachment model of smectic type clusters of BC molecules surrounding the microparticle is presented.

Spontaneous achiral symmetry breaking in liquid crystalline phases.

It is well known that spontaneous deracemization or spontaneous chiral resolution occasionally occurs when racemic molecules are crystallized. However, it is not easy to believe such phenomenon will occur when forming liquid crystal phases. Spontaneous chiral domain formation is introduced, when molecules form particular liquid crystal phases. Such molecules possess no chiral carbon but may have axial chirality. However, the potential barrier between two chiral states is low enough to allow mutual transformation even at room temperature. Therefore the systems are essentially not racemic but nonchiral or achiral. First, enhanced chirality by doping chiral nematic liquid crystals with nonchiral molecules is described. Emphasis is made on ester molecules for their anomalous behavior. Second, spontaneous chiral resolution is discussed. Three examples with rod-, bent-, and disk-shaped molecules are shown to give such phenomena. Particular attention will be paid to controlling enantiomeric excess (ee). Actually, almost 100% ee was obtained by applying some external chiral stimuli. This is very noteworthy in the sense that we can create chiral molecules (chiral field) without using any chiral species.

High-resolution calorimetric study of phase transitions in chiral smectic-C liquid crystalline phases.

We carried out an improved characterization of phase transitions among chiral smectic-C subphases observed for various antiferroelectric liquid crystals by precise heat capacity measurements. It was found that the phase transitions are intrinsically first order exhibiting a remarkable heat anomaly which involves little pretransitional thermal fluctuation and a finite thermal hysteresis. On the other hand, we also noticed that the critical point of the smectic-C(α)(*)-smectic-C* transition is induced by the destabilization of the smectic-C(α)(*) phase which couples with the fluctuation associated with the smectic-A-smectic-C(α)(*) phase transition.

Distinctive thermal behavior and nanoscale phase separation in the heterogeneous liquid-crystal B4 matrix of bent-core molecules.

By means of high-resolution calorimetry, we studied thermodynamic properties of the liquid-crystal B(4) phase where bent-core molecules form a helical nanofilament structure. Distinctive thermal behavior characterizing the growth process of the B(4) phase was obtained in undergoing the phase transition with many sharp peaks, indicating a highly heterogeneous structure. It has been demonstrated that such unusual behavior is commonly seen for two types of rodlike molecules as well as for various mixture compositions. We speculate that mixture systems involve a nanoscale phase-separated structure due to the remarkable aggregation effect in the bent-core molecules and that the helical nanofilament structure independently grows in the isotropic state of rodlike molecules. We also propose that the asymmetry in viscoelastic property plays a role in yielding unusual behavior.

Calorimetric study of the effect of bent-shaped dopant molecules on the critical behavior at the nematic-smectic-Ad phase transition.

We report results of calorimetric studies for the binary mixture of rodlike host n-alkyloxy-cyanobiphenyl (nOCB, n=8,9) and bent-shaped guest 1,3-phenylene-bis[4-(3-methylbenzoyloxy)]-4'-n-dodecylbiphenyl-4'-carboxylate (BC12). The effect of bent-shaped dopant molecules on the critical behavior associated with the nematic-smectic-A(d) phase transition has been studied in detail. The transition temperature for the nematic-smectic-A(d) phase sharply decreases as the increase of the mole fraction of the dopant concentration (denoted X for the BC12/9OCB mixture and Y for the BC12/8OCB mixture). The dependence of the critical exponent α on X and Y is well explained in terms of the McMillan ratio. A nearly tricritical exponent has been obtained for the X=0.01 mixture. X=0.02-0.03 mixtures, pure 8OCB, and Y=0.01-0.03 mixtures exhibit nonuniversal behaviors with effective exponents lying between the 3D-XY and tricritical exponents. The heat capacity anomaly for Y=0.05 has been well described with the 3D-XY exponent. The critical amplitude ratio A(-)/A(+) is close to 1 and insensitive to the dopant concentration. No Fisher renormalization of the critical exponent has been observed even for nearly tricritical compositions, which indicates the smallness of the concentration plays a decisive role rather than the steepness of the N-SmA(d) phase boundary.

Critical behavior at transitions from uniaxial to biaxial phases in a smectic liquid-crystal mixture.

We report results of calorimetric and optical investigations of binary mixtures of rodlike and bent-shaped molecules. We find that the observed critical heat anomaly associated with the smectic-A2 to biaxial smectic-A2b transition is well described with a Fisher-renormalized form of the usual scaling expression. The effect of renormalization is large in this system in part because of the moderately steep slope of the phase boundary (dT(c)/ dX∼100 K, where X is the mole fraction of the bent-core molecules) and in part because of the proximity to the tricritical point. The magnitude of heat anomaly at the smectic-A2-smectic-A2b transition showed a drastic decrease as X becomes smaller. Moreover, the nematic-smectic-A2 transitions investigated turned out to be always first order and the transition enthalpy showed only weak dependence on the concentration X. The results imply that the energy fluctuations around the smectic-A2-smectic-A2b transition are very sensitive to the underlying ordering of the smectic-A2 background.

Splay bend elasticity of a bent-core nematic liquid crystal.

We measured the splay (K11) and bend (K33) elastic constants in the nematic phase of a bent-core liquid crystal. In the vicinity of the nematic-isotropic transition temperature K33 is proportional to the square of the order parameter. In the nematic range K11 increases monotonically with decreasing temperature, whereas K33 is practically independent of temperature and is smaller than K11 . K33 exhibits a pretransitional slow divergence toward the transition temperature to the smectic phase and becomes slightly larger than K11. The small K33 is explained on the basis of strong coupling of the bent shape of the molecules with the bend distortion.

Quasi-two-dimensional Ising critical behavior of de Vries liquid crystals observed in the heat capacity and dielectric response.

Heat capacity and dielectric measurements have been made on a liquid crystal compound exhibiting de Vries type of smectic-A{*} (Sm-A{*}) phase. Heat capacity shows a significant anomaly which is almost symmetric for above and below the Sm-A{*}-Sm-C{*} transition temperature. The transition was found to be very weakly first order. The critical exponent gamma determined from the dielectric data lies 1.8+/-0.2. The present heat capacity data as well as former data for another compound of de Vries type have been analyzed in detail. It was found that the heat capacity data for both compounds are fitted well with a logarithmic divergence except in the immediate vicinity of the transition. These results agree with an expectation that de Vries Sm-A{*}-Sm-C-{*} transition can exhibit quasi-two-dimensional Ising critical behavior.

Crystal structures and transistor properties of phenyl-substituted tetrathiafulvalene derivatives.

The crystal structures, thin-film properties, and field-effect transistor (FET) characteristics of tetrathiafulvalene (TTF) derivatives with two phenyl groups are systematically investigated. The highest mobility, 0.11 cm(2) V(-1) s(-1), is observed in biphenyl-substituted TTF (1). The correlation between the crystal structures and the FET properties demonstrates that good transistor properties are associated with two-dimensional intermolecular interaction, which is achieved when the molecules are standing nearly perpendicular to the substrate. Since these TTF derivatives are strong electron donors, the use of a metallic charge-transfer salt (TTF)(TCNQ) as the source and drain electrodes has resulted in a considerable reduction of the off current (TCNQ: tetracyanoquinodimethane).

Appearance of a liquid crystalline nematic-isotropic critical point in a mixture system of rod- and bent-shaped molecules.

Heat capacity measurements have been made on a liquid-crystal mixture system formed from bent-shaped molecule 1,3-phenylene bis[4-(4-8-alkoxyphenyliminomethyl)benzoates] (P-8-O-PIMB) and rod-shaped molecule n-pentyl-cyanobiphenyl (5CB). The obtained results can be understood assuming that the addition of P-8-O-PIMB molecules to the 5CB system affects as a field conjugate to the nematic order parameter. The B(X)-B(4) transition can be viewed as the nematic-isotropic transition of 5CB, which is embedded in a framework of the B(4) structure of P-8-O-PIMB molecules. The present mixture system offers a rare example of the nematic-isotropic critical point, whose critical behavior has not been studied yet in detail.

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.

Enhanced chirality by adding achiral molecules into the chiral system.

It is generally accepted that the doping of chiral materials with achiral molecules diminishes the chirality of the system. Here we report the opposite phenomenon. It was found that the structural chirality of smectic phases made of rodlike molecules, Sm-C(*) or Sm-C(*)(A) phases, measured as the reverse length of the helical pitch, is enhanced by adding small amount of achiral bent-shaped molecules. The effect is due to the chirality transfer between host and guest systems. Achiral bent-shaped molecules become structurally chiral due to the interactions with the chiral host that induces tilt and polar order of bent-shaped molecules. This induced chirality is then transferred back to the host.

Patterns in hybrid nematic liquid-crystal films: topography and topology.

Spontaneous pattern formation in hybrid nematic liquid-crystal films on glycerol was studied with both polarized transmission and unpolarized monochromatic reflected light microscopy. These observations reveal that the patterns that are found in 1 to 10-microm-thick films are due to a combination of film topography, gradients in film thickness that act as an aligning field, and topology, connectivity requirements on the vector field. The patterns studied include cellular patterns, disclinations connected by 2pi-walls, and 2pi-walls that narrow to a point at the edge of the films.

Holes and disclinations in hybrid nematic liquid crystal films.

Defect patterns in hybrid nematic liquid crystal films of pentylcyanobiphenyl (5CB) on a glycerol surface were studied with polarized transmission and monochromatic reflected light microscopy. We report that disclinations of apparent topological strength zero, stable pairs of +1 and -1 disclinations, and higher strength defects found in these films are stabilized by holes in the liquid crystal film. These holes are produced by a monolayer of surfactant on the glycerol surface. In addition, we describe the topology of the director field in the film during the coalescing of two such holes.

Observation of a soft smectic liquid-crystal phase in a mixture showing V-shaped switching.

We present the experimental observation of a soft smectic liquid crystal phase in a three-component liquid crystal mixture reported to exhibit V-shaped switching. Unlike the layer compression modulus B of the usual smectic phase, B of the soft smectic phase has a peculiar temperature and frequency dependence. It was found that this characteristic feature is one of the main driving force to realize an ideal V-shaped switching.

Special phase matching of second-harmonic generation in helical ferroelectric liquid crystal cells.

The helical structures in ferroelectric liquid crystals can be utilized to realize a special phase matching for second-harmonic generation (SHG) when two counter fundamental waves propagate along the helical axis and the wavelength of SHG is near the photonic (selective reflection) band edge. On the basis of the exact theory [Drevensek-Olenik and Copic, Phys. Rev. E 56, 581 (1997)], a simple analytical description is derived and some characteristic features of the special phase matching are shown. (1) Special phase matching is definitely achieved under particular combinations of polarization. (2) The SH spectrum is related to a subsidiary oscillating structure in the selective reflection spectrum. The maximum SH intensity is realized at the first dip of the oscillation near one of the edges in the selective reflection band. (3) The thickness (d) dependence of the maximum SH intensity is d4 in thick cells, while it is d2 for conventional phase matching. (4) The linewidth for the SH peak is d(-3) dependent, which is much narrower than in conventional phase matching.

Molecular orientation near the surface of a smectic liquid crystal cell showing V-shaped switching by means of attenuated total internal reflection ellipsometry.

Attenuated total internal reflection ellipsometry was used to probe the molecular orientation and switching near the surface of a smectic liquid crystal cell showing V-shaped switching. We find that the switching occurs collectively near the surface as in the bulk. The molecules form a twisted state, but the twist angle relative to the bulk layer normal is small because of compensating twist of the smectic layer normal. As a result, a rather uniform molecular orientation is produced, resulting in high extinction and a high contrast ratio in the absence of a field.