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.

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.

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.

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.

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.

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.

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.

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.

Observation of a possible tetrahedratic phase in a bent-core liquid crystal.

An experimental study of the heat capacity, mass density, magnetic-field-induced optical birefringence, linewidth and intensity of scattered light, and the viscosities associated with nematic order parameter fluctuations and fluid flow has been performed on an achiral bent-core liquid crystal above its clearing point temperature. The measurements reveal a transition between two optically isotropic phases that is consistent with recent theoretical predictions of a "tetrahedratic" form of orientational order.

Three-dimensional imaging of dielectric patterns in electrohydrodynamic convection of a nematic liquid crystal.

The transition from surface to bulk normal dielectric rolls in a nematic liquid crystal is imaged by fluorescence confocal polarizing microscopy. The three-dimensional director structure and the liquid flow are scanned in both the layer plane and the transverse plane. Two systems of small-scale convective flow are formed, one at each electrode. Strong anchoring makes director oscillations difficult and charges accumulate by the Carr-Helfrich mechanism. The middle region is a structureless convection where the director oscillates with the frequency of the applied voltage. The small-scale flow eventually fills the cell from one electrode to the other as one system of thin and elongated rolls. The true dielectric mode is not a director pattern, rather a surface flow instability.

Critical behavior at the isotropic-to-nematic phase transition in a bent-core liquid crystal.

Magnetic birefringence and dynamic light scattering measurements of orientational order parameter fluctuations at the isotropic-nematic phase transition of a bent-core liquid crystal reveal a pretransitional temperature dependence consistent with the standard Landau-deGennes mean field theory. However, as follows: the transition in the bent-core compound is more weakly first order (TNI-T* approximately 0.4 degrees C), the leading Landau coefficient is approximately 30 times lower, the viscosity associated with nematic order fluctuations is approximately 10 times higher, and the density change is approximately 10 times lower, than typically observed in calamitic (rod-shaped) liquid crystals. One consistent explanation for these anomalies is an optically isotropic phase composed of microscopic complexes or "clusters" of bent-core molecules.

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.

Nonstandard electroconvection in a bent-core nematic liquid crystal.

We characterize three nonstandard electrohydrodynamic instabilities in nematic liquid crystals composed of bent-core molecules. In addition to their shape, another important attribute of this material is that the anisotropy in the electrical conductivity changes sign as the frequency of the applied electric field changes. These instabilities do not appear to fit within the standard model for electroconvection. The first instability creates a pattern with stripes parallel to the initial director orientation, with a wavelength about equal to the separation of the cell plates. The next is the previously reported prewavy instability. The third instability is optically and dynamically identical to the prewavy instability, but is distinguished by different threshold behavior.

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.

Charge transport measurement during turbulent electroconvection.

We report measurements of the energy dissipation during electroconvection of a nematic liquid crystal in the fully turbulent regime. The energy dissipation is quantified by measuring the electric current at constant potential difference. In certain cases, we observe the surprising result that the dimensionless energy dissipation ceases to increase with increasing potential difference. In some circumstances, a power-law scaling relationship between the dimensionless excess energy dissipation and the reduced voltage is observed, but the exponent in this relationship varies dramatically with both the time scale of the driving electric field and the separation between the electrodes.

Length and speed selection in dendritic growth of electrohydrodynamic convection in a nematic liquid crystal.

We present results on dendritic growth of electrohydrodynamic convection in a nematic liquid crystal subject to parallel magnetic and electric fields. Previous work found that these dendrites have many properties in common with crystalline dendrites. Nevertheless, crystalline dendrites are significantly different from the system studied here. Specifically, the length selection mechanism for these dendrites is substantially richer than that which controls crystalline dendritic growth. In contrast with the sharp selection mechanism operating in the case of crystalline dendrites, these dendrites show only partial selection. As the separation between electrodes and the magnetic field becomes larger, the selection becomes even less sharp. We quantify the selection by measuring two important characteristics of these dendrites, their length scale, as reflected by the tip radius of curvature, and their growth speed. We measure these quantities as functions of the most important control parameters: the spacing of the liquid crystal cell, the magnetic field, and the applied voltage. A nontrivial scaling relationship is found for the tip radius of curvature. These dendrites occur in a system containing only one state of matter, and they are defined not by an abrupt boundary but by a diffuse interface. We find that the width of that interface is determined solely by the applied magnetic field.

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.

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.

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.