Dynamics of coreless defects during winding up transitions in confined chiral nematic liquid crystals.

Twist-coupled elastic deformations are ubiquitous and in the limelight of interest for next-generation self-shaping materials. Here, we describe how twist dynamics under fixed anchoring lead to bend deformation and defect dynamics in a field-unwound chiral liquid crystal material. We use the Q-tensor dynamics under the Landau-de Gennes formalism in a finite-element mesh to explore the texture pathways from the unwound (homeotropic) to the helical planar structure. Our simulations describe well previously reported experiments and confirm that the process occurs by forming pairs of coreless defects that interact with each other and create quadrupolar structures called Lehmann clusters. The dynamics and coarsening of dipoles and quadrupoles of defects are described. This numerical study describes the full dynamics, which has been sought for several years.

The interplay between spatial and heliconical orientational order in twist-bend nematic materials.

The helical pitch formed by organic molecules, such as the α-helix of proteins, usually requires hydrogen bonding between chiral units and long-range positional order. It was recently found that certain liquid crystal oligomers can have a twist-bend nematic (NTB) phase with nanoscale heliconical structure without hydrogen bonding, molecular chirality or positional order. To understand the nature of this unique structure, here we present hard and resonant tender X-ray scattering studies of two novel sulfur containing dimer materials. We simultaneously measure the temperature dependences of the helical pitch and the correlation length of both the helical and positional order. In addition to an unexpected strong variation of the pitch with the length of the spacer connecting the monomer units, we find that at the transition to the NTB phase the positional correlation length drops. The helical structure was found not only in the NTB phase but observed even in the upper range of a smectic phase that forms just below the NTB state. The coexistence of smectic layering and the heliconical order indicates a layered (SmATB) phase wherein the rigid units of the dimers are tilted with respect to the smectic layer normal in order to accommodate the bent conformation of the dimers and the tilt direction rotates along the heliconical axis.

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.

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.

Mesophase structure and behaviour in bulk and restricted geometry of a dimeric compound exhibiting a nematic-nematic transition.

We present structural studies of a dimeric compound composed of a central heptyl spacer linking two mesogens consisting of terphenyl units at which two adjacent fluoro groups are attached to each central ring. The terminal rings are linked to pentyl chains as terminal groups. The material exhibits a nematic-nematic transition and a low temperature modulated phase. The higher temperature nematic phase was found to exhibit an anomaly of the bend elastic constant similar to that of the dimers with N-Ntb phase sequence, and the physical properties of the low-temperature nematic phase are similar to those of the known Ntb materials. The structure of the low-temperature modulated smectic/columnar phase is described together with its ability to form freely suspended films and fibres. The relation of the modulated structure to the fibre formation and to the appearance of the labyrinthine instability in freely-suspended films is discussed.

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.

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.

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.

Nanostructure of Edge Dislocations in a Smectic-C* Liquid Crystal.

We report on the first direct nanoscale imaging of elementary edge dislocations in a thermotropic smectic-C* liquid crystal with the Burgers vector equal to one smectic layer spacing d. We find two different types of dislocation profiles. In the dislocation of type A, the layers deformations lack mirror symmetry with respect to the plane perpendicular to the Burgers vector; the dislocation core size is on the order of d. In the dislocation of type S, the core is strongly anisotropic, extending along the Burgers vector over distances much larger (by a factor of 4) than d. The difference is attributed to a different orientation of the molecular tilt plane with respect to the dislocation's axis; the asymmetric layers distortions are observed when the molecular tilt plane is perpendicular to the axis and the split S core is observed when the molecules are tilted along the line.

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.

Helical nanofilaments of bent-core liquid crystals with a second twist.

The B4 phase of bent-core liquid crystals has been shown to be an assembly of twisted layers stacked to form helical nanofilaments. Interestingly, some of them have structural colours that cannot be explained by the nanofilaments alone. Here cryogenic-transmission electron microscopy observations on 40-120 nm films of four bent-core liquid crystal materials show that the filaments are present even in contact with a carbon substrate with only minor deformation, thus representing bulk properties. We find that the subsequent arrays of nanofilaments are not parallel to each other, but rotate by an angle of 35-40° with respect to each other. This doubly twisted structure can explain the structural colour. Being principally different from the packing of molecules in the twist grain boundary and blue phases, the double-twist structure of helical nanofilaments expands the rich word of nanostructured organic materials.

Nematic twist-bend phase with nanoscale modulation of molecular orientation.

A state of matter in which molecules show a long-range orientational order and no positional order is called a nematic liquid crystal. The best known and most widely used (for example, in modern displays) is the uniaxial nematic, with the rod-like molecules aligned along a single axis, called the director. When the molecules are chiral, the director twists in space, drawing a right-angle helicoid and remaining perpendicular to the helix axis; the structure is called a chiral nematic. Here using transmission electron and optical microscopy, we experimentally demonstrate a new nematic order, formed by achiral molecules, in which the director follows an oblique helicoid, maintaining a constant oblique angle with the helix axis and experiencing twist and bend. The oblique helicoids have a nanoscale pitch. The new twist-bend nematic represents a structural link between the uniaxial nematic (no tilt) and a chiral nematic (helicoids with right-angle tilt).

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.

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.

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.

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.