Pretransitional behavior of viscoelastic parameters at the nematic to twist-bend nematic phase transition in flexible n-mers.

We report dynamic light scattering measurements of the orientational (Frank) elastic constants and associated viscosities among a homologous series of a liquid crystalline dimer, trimer, and tetramer exhibiting a uniaxial nematic (N) to twist-bend nematic (NTB) phase transition. The elastic constants for director splay (K11), twist (K22) and bend (K33) exhibit the relations K11 > K22 > K33 and K11/K22 > 2 over the bulk of the N phase. Their behavior near the N-NTB transition shows dependency on the parity of the number (n) of the rigid mesomorphic units in the flexible n-mers. Namely, the bend constant K33 in the dimer and tetramer turns upward and starts increasing close to the transition, following a monotonic decrease through most of the N phases. In contrast, K33 for the trimer flattens off just above the transition and shows no pretransitional enhancement. The twist constant K22 increases pretransitionally in both even and odd n-mers, but more weakly so in the trimer, while K11 increases steadily on cooling without evidence of pretransitional behavior in any n-mer. The viscosities associated with pure splay, twist-dominated twist-bend, and pure bend fluctuations in the N phase are comparable in magnitude to those of rod-like monomers. All three viscosities increase with decreasing temperature, but the bend viscosity in particular grows sharply near the N-NTB transition. The N-NTB pretransitional behavior is shown to be in qualitative agreement with the predictions of a coarse-grained theory, which models the NTB phase as a "pseudo-layered" structure with the symmetry (but not the mass density wave) of a smectic-A* phase.

Magnetically tunable selective reflection of light by heliconical cholesterics.

We present studies of chiral nematic liquid crystals composed of flexible dimer molecules subject to large dc magnetic fields between 0 and 31 T. We observe that these fields lead to selective reflection of light depending on temperature and magnetic field. The band of reflected wavelengths can be tuned from ultraviolet to beyond the IR-C band. A similar effect induced by electric fields has been presented previously, and was explained by a field-induced oblique-heliconical director deformation in accordance with early theoretical predictions. The use of magnetic field here instead of electric field allows precise measurements of some material constants and holds promise for wireless tuning of selective reflection.

Light scattering study of the "pseudo-layer" compression elastic constant in a twist-bend nematic liquid crystal.

The nematic twist-bend (TB) phase, exhibited by certain achiral thermotropic liquid crystalline (LC) dimers, features a nanometer-scale, heliconical rotation of the average molecular long axis (director) with equally probable left- and right-handed domains. On meso to macroscopic scales, the TB phase may be considered as a stack of equivalent slabs or "pseudo-layers", each one helical pitch in thickness. The long wavelength fluctuation modes should then be analogous to those of a smectic-A phase, and in particular the hydrodynamic mode combining "layer" compression and bending ought to be characterized by an effective layer compression elastic constant Beff and average director splay constant K. The magnitude of K is expected to be similar to the splay constant of an ordinary nematic LC, but due to the absence of a true mass density wave, Beff could differ substantially from the typical value of ∼106 Pa in a conventional smectic-A. Here we report the results of a dynamic light scattering study, which confirms the "pseudo-layer" structure of the TB phase with Beff in the range 103-104 Pa. We show additionally that the temperature dependence of Beff at the TB to nematic transition is accurately described by a coarse-grained free energy density, which is based on a Landau-deGennes expansion in terms of a heli-polar order parameter that characterizes the TB state and is linearly coupled to bend distortion of the director.

Anomalous Increase in Nematic-Isotropic Transition Temperature in Dimer Molecules Induced by a Magnetic Field.

We have determined the nematic-isotropic transition temperature as a function of an applied magnetic field in three different thermotropic liquid crystalline dimers. These molecules are comprised of two rigid calamitic moieties joined end to end by flexible spacers with odd numbers of methylene groups. They show an unprecedented magnetic field enhancement of nematic order in that the transition temperature is increased by up to 15 K when subjected to a 22 T magnetic field. The increase is conjectured to be caused by a magnetic-field-induced decrease of the average bend angle in the aliphatic spacers connecting the rigid mesogenic units of the dimers.

Second harmonic light scattering induced by defects in the twist-bend nematic phase of liquid crystal dimers.

The nematic twist-bend (NTB) phase, exhibited by certain thermotropic liquid crystalline (LC) dimers, represents a new orientationally ordered mesophase - the first distinct nematic variant discovered in many years. The NTB phase is distinguished by a heliconical winding of the average molecular long axis (director) with a remarkably short (nanoscale) pitch and, in systems of achiral dimers, with an equal probability to form right- and left-handed domains. The NTB structure thus provides another fascinating example of spontaneous chiral symmetry breaking in nature. The order parameter driving the formation of the heliconical state has been theoretically conjectured to be a polarization field, deriving from the bent conformation of the dimers, that rotates helically with the same nanoscale pitch as the director field. It therefore presents a significant challenge for experimental detection. Here we report a second harmonic light scattering (SHLS) study on two achiral, NTB-forming LCs, which is sensitive to the polarization field due to micron-scale distortion of the helical structure associated with naturally-occurring textural defects. These defects are parabolic focal conics of smectic-like "pseudo-layers", defined by planes of equivalent phase in a coarse-grained description of the NTB state. Our SHLS data are explained by a coarse-grained free energy density that combines a Landau-deGennes expansion of the polarization field, the elastic energy of a nematic, and a linear coupling between the two.

Polar structure of disclination loops in nematic liquid crystals probed by second-harmonic-light scattering.

Angle-resolved, second-harmonic-light scattering (SHLS) measurements are reported for three different classes of thermotropic nematic liquid crystals (NLCs): polar and nonpolar rodlike compounds and a bent-core compound. Results revealing well-defined scattering peaks are interpreted in terms of the electric polarization induced by distortions of the nematic orientational field ("flexopolarity") associated with inversion wall defects, nonsingular disclinations, analogous to Neel walls in ferromagnets, that often exhibit a closed loop morphology in NLCs. Analysis of the SHLS patterns based on this model provides a "proof-of-concept" for a potentially useful method to probe the flexopolar properties of NLCs.

Twist-bend nematic liquid crystals in high magnetic fields.

We present magneto-optic measurements on two materials that form the recently discovered twist-bend nematic (N_{tb}) phase. This intriguing state of matter represents a fluid phase that is orientationally anisotropic in three directions and also exhibits translational order with periodicity several times larger than the molecular size. N_{tb} materials may also spontaneously form a visible, macroscopic stripe texture. We show that the optical stripe texture can be persistently inhibited by a magnetic field, and a 25T external magnetic field depresses the N-N_{tb} phase transition temperature by almost 1{∘}C. We propose a quantitative mechanism to account for this shift and suggest a Helfrich-Hurault-type mechanism for the optical stripe formation.

Magnetic-field-induced suppression of the amorphous blue phase.

We present magneto-optical measurements on two liquid crystals that exhibit a wide temperature-range amorphous blue phase (BPIII). Magnetic fields up to 25 T are found to suppress the onset of BPIII in both materials by almost 1 °C. This effect appears to increase nonlinearly with the field strength. The effect of high fields on established BPIIIs is also reported, in which we find significant hysteresis and very slow dynamics. Possible explanations of these results are discussed.

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.

Light scattering from liquid crystal director fluctuations in steady magnetic fields up to 25 tesla.

We report on homodyne dynamic light scattering measurements of orientational fluctuation modes in both calamitic and bent-core nematic liquid crystals, carried out in the new split-helix resistive magnet at the National High Magnetic Field Laboratory. The relaxation rate and inverse scattered intensity of director fluctuations exhibit a linear dependence on field-squared up to 25 tesla, which is consistent with strictly lowest order coupling of the tensor order parameter Q to field (Q(αß)B(α)B(ß)) in the nematic free energy. However, we also observe evidence of field dependence of certain nematic material parameters, an effect which may be expected from the mean field scaling of these quantities with the magnitude of Q and the predicted variation of Q with field.

Dielectric technique to measure the twist elastic constant of liquid crystals: the case of a bent-core material.

The effect of director pretilt on the twist magnetic Fréedericksz transition of nematics was investigated in a planar cell. The director configuration was calculated as a function of magnetic inductance. The dielectric and optical response of the nematic liquid crystal was numerically modeled. A dielectric measurement method for determining the elastic constant K_{22} is presented. The influence of the conditions for the Mauguin effect is discussed. The theoretical predictions were confirmed by our experiments. Experimental data for all elastic constants of a bent-core nematic material are presented and discussed.

Biaxial nematic order induced by smectic fluctuations.

We report on a series of measurements on the microscopic structure and the magneto-optical properties of a calamitic liquid crystalline compound in its nematic phase. Structural studies show the existence of short-range, tilted smectic order consistent with pretransitional effects above an underlying smectic phase. Concomitantly, magneto-optical results exhibit the existence of an optic axis not collinear with the uniaxial director. This apparent biaxial nature is discussed within the context of coupling between the tensor nematic and the smectic order parameters.

Elasticity of lyotropic chromonic liquid crystals probed by director reorientation in a magnetic field.

Using a magnetic Frederiks transition technique, we measure the temperature and concentration dependences of splay K1, twist K2, and bend K3 elastic constants for the lyotropic chromonic liquid crystal sunset yellow formed through noncovalent reversible aggregation of organic molecules in water. K1 and K3 are comparable to each other and are an order of magnitude higher than K2. At higher concentrations and lower temperatures, K1 and the ratios K1/K3 and K1/K2 increase, which is attributed to elongation of self-assembled lyotropic chromonic liquid crystal aggregates, a feature not found in conventional thermotropic and lyotropic liquid crystals formed by covalently bound units of a fixed length.

Magneto-optical technique for detecting the biaxial nematic phase.

The existence of the elusive biaxial phase has been the subject of much discussion since it was predicted by Freiser in 1970. More recently, there have been numerous attempts to find a thermotropic liquid crystal that exhibits a biaxial phase and with this, conflicting reports about whether such a phase has been positively identified in bent-core liquid crystals. One reason for the discrepancy is that there is currently no way to rule out surface effects or anchoring transitions, both of which may give a false positive identification of a uniaxial-biaxial nematic transition. We have developed a technique that uses a magnetic field to align the uniaxial director, thus widening its application to any bent-core nematic material.

Nanostructures of liquid crystal phases in mixtures of bent-core and rod-shaped molecules.

We report small angle x-ray scattering (SAXS) studies of isotropic, nematic, and smectic mesophases formed by binary mixtures of bent-core (BC) and rod-shaped (RS) molecules. While optical studies indicate that the components are fully miscible, SAXS reveals fascinating structures that are consistent with segregation on a nanoscopic scale. We find that tilted smectic clusters, which have been previously reported in both the nematic and isotropic states of the pure BC materials, are also present in mixtures with up to 50 wt% of the RS compound; this is consistent with previous dielectric and flexoelectric studies on such mixtures. Unexpectedly in this concentration range the clusters are present in the isotropic and in the induced smectic phase range, as well as throughout the nematic phase. The results in the smectic phase also reveal complex layering phenomena, providing important insight into the interaction between bent and rod-shaped molecules. These studies will be crucial in the design of promising new functional nanomaterials.

Elastic constants and orientational viscosities of a bent-core nematic liquid crystal.

Using a combination of dynamic light scattering and Freedericksz transitions induced in applied magnetic and electric fields, we have determined the absolute magnitudes of the Frank elastic constants and effective orientational viscosities of the bent-core nematic liquid crystal, 4-chloro-1,3-phenylene bis 4-[4'-(9-decenyloxy)benzoyloxy] benzoate. At a fixed temperature 2 °C below the isotropic-nematic transition, we find K11 = 3.1 x 10⁻¹² N, K22 = 0.31 x 10⁻¹² N, K33 = 0.88 x 10⁻¹² N, η{splay}=1.1 Pa s, η{twist}=0.37 Pa s, and η{bend}=1.2 Pa s. The unusual anisotropies of these parameters are discussed in terms of short-range, smectic-C-like correlations among molecules in the nematic phase.

Diagnosis of spatiotemporal chaos in wave envelopes of a nematic electroconvection pattern.

In this paper we report and analyze complex spatiotemporal dynamics recorded in electroconvection in the nematic liquid crystal I52, driven by an ac voltage slightly above the onset value. The instability mechanism creating the pattern is an oscillatory (Hopf) instability, giving rise to two pairs of counterpropagating rolls traveling in oblique directions relative to the unperturbed director axis. If a system of nonlinear partial differential equations shows the same set of unstable modes, the pattern above the onset is represented in a weakly nonlinear analysis as a superposition of the traveling rolls in terms of wave envelopes varying slowly in space and time. Motivated by this procedure, we extract slowly varying envelopes from the space-time data of the pattern, using a four-wave demodulation based on Fourier analysis. In order to characterize the spatiotemporal dynamics, we apply a variety of diagnostic methods to the envelopes, including the calculation of mean intensities and correlation lengths, global and local Karhunen-Loève decompositions in Fourier space and physical space, the location of holes, the identification of coherent vertical structures, and estimates of Lyapunov exponents. The results of this analysis provide strong evidence that our pattern exhibits extensive spatiotemporal chaos. One of its main characteristics is the presence of coherent structures of low and high intensities extended in the vertical (parallel to the director) direction.

Large flow birefringence of nematogenic bent-core liquid crystals.

We have found that bent-core liquid crystalline materials show exceptionally large intrinsic flow birefringence in their isotropic liquid phase. This effect is more than 100 times larger than typical values measured for low molecular weight liquid crystals. The specific flow birefringence (i.e., normalized by the flow viscosity) is an order of magnitude larger than in both side-chain polymeric as well as low molecular weight liquid crystals. We propose that this large enhancement for bent-core compounds may be attributed to nanoscale smecticlike clusters that persist above the nematic-isotropic transition temperature, and shear align under shear flow; however, this mechanism has not yet been definitively confirmed.

Magnetic-field induced isotropic to nematic liquid crystal phase transition.

We report on measurements of magnetic-field induced nematic order in the bent-core liquid crystal 4-chlororesorcinol bis[4-(4-n-dodecyloxybenzoyloxy) benzoate]. Using the 31 T solenoid at the National High Magnetic Field Laboratory, we have observed, at temperatures less than 1 degrees above the clearing point, a first-order transition to the nematic phase. The critical magnetic field at which this occurs increases with temperature. We discuss these results within the context of both Maier-Saupe and Landau-de Gennes mean-field models for the nematic-isotropic transition. The implications of possible tetrahedratic order are also discussed. To our knowledge, this is the first observation of such a magnetic-field induced transition in a thermotropic liquid crystal; the reasons for which this behavior is now attainable are discussed.

Converse flexoelectric effect in a bent-core nematic liquid crystal.

Flexoelectricity is a unique property of liquid crystals; it is a linear coupling between electric polarizations and bend and/or splay distortions of the direction of average molecular orientation. Recently it was shown [J. Harden, Phys. Rev. Lett. 97, 157802 (2006)] that the bend flexoelectric coefficient in bent-core nematic liquid crystals can be three orders of magnitude higher than the effect with calamitic (rod-shaped) molecular shape. Here we report the converse of the flexoelectric effect: An electric field applied across a bent-core liquid crystal sandwiched between thin flexible substrates produces a director distortion which is manifested as a polarity-dependent flexing of the substrates. The flex magnitude is shown to be consistent with predictions based upon both the measured value of the bend flexoelectric constant and the elastic properties of the substrates. Converse flexoelectricity makes possible a new class of microactuators with no internal moving parts, which offers applications as diverse as optical beam steering to artificial muscles.