Nematic Liquid Crystal Phase Research Articles

Mid-infrared photothermal heterodyne spectroscopy in a liquid crystal using a quantum cascade laser.

We report a technique to measure the mid-infrared photothermal response induced by a tunable quantum cascade laser in the neat liquid crystal 4-octyl-4'-cyanobiphenyl (8CB), without any intercalated dye. Heterodyne detection using a Ti:sapphire laser of the response in the solid, smectic, nematic and isotropic liquid crystal phases allows direct detection of a weak mid-infrared normal mode absorption using an inexpensive photodetector. At high pump power in the nematic phase, we observe an interesting peak splitting in the photothermal response. Tunable lasers that can access still stronger modes will facilitate photothermal heterodyne mid-infrared vibrational spectroscopy.

Brownian dynamics and dynamic Monte Carlo simulations of isotropic and liquid crystal phases of anisotropic colloidal particles: A comparative study

We report on the diffusion of purely repulsive and freely rotating colloidal rods in the isotropic, nematic, and smectic liquid crystal phases to probe the agreement between Brownian and Monte Carlo dynamics under the most general conditions. By properly rescaling the Monte Carlo time step, being related to any elementary move via the corresponding self-diffusion coefficient, with the acceptance rate of simultaneous trial displacements and rotations, we demonstrate the existence of a unique Monte Carlo time scale that allows for a direct comparison between Monte Carlo and Brownian dynamics simulations. To estimate the validity of our theoretical approach, we compare the mean square displacement of rods, their orientational autocorrelation function, and the self-intermediate scattering function, as obtained from Brownian dynamics and Monte Carlo simulations. The agreement between the results of these two approaches, even under the condition of heterogeneous dynamics generally observed in liquid crystalline phases, is excellent.

Polymerization of Thiophene Derivatives Bearing Bulky Azobenzene Substituent with Flexible Alkyl Spacer in Liquid Crystal

A series of polythiophene derivatives bearing azobenzene moiety has been synthesized in liquid crystal (LC) as a reaction medium. Infrared absorption, ultra violet-visible (UV-vis) absorption, fluorescence spectroscopies, and gel permeation chromatography for the polymers thus prepared are examined. LC temperature ranges of the reaction mixtures before and after polymerization are confirmed with differential scanning calorimetry (DSC) and visual inspection using polarizing optical microscopy (POM) to achieve polymerization in the LC temperature range. The LC medium free polymers show nematic LC phase.

Flexoelectric coefficient measurements in the nematic liquid crystal phase of 5CB

We report measurements of the bulk flexoelectric coefficient (e1 − e3) of 5CB (4-Cyano-4′-pentylbiphenyl), in the temperature range 20–34 °C, with a relative combined standard uncertainty of 2 %. The chiral flexoelectro-optic method was used with 1 wt % high-twisting-power chiral additive. At 25 °C, (e1 − e3) = 7.10 pC/m with a combined standard uncertainty of 0.14 pC/m.

Liquid-crystal-mediated self-assembly at nanodroplet interfaces

Technological applications of liquid crystals have generally relied on control of molecular orientation at a surface or an interface. Such control has been achieved through topography, chemistry and the adsorption of monolayers or surfactants. The role of the substrate or interface has been to impart order over visible length scales and to confine the liquid crystal in a device. Here, we report results from a computational study of a liquid-crystal-based system in which the opposite is true: the liquid crystal is used to impart order on the interfacial arrangement of a surfactant. Recent experiments on macroscopic interfaces have hinted that an interfacial coupling between bulk liquid crystal and surfactant can lead to a two-dimensional phase separation of the surfactant at the interface, but have not had the resolution to measure the structure of the resulting phases. To enhance that coupling, we consider the limit of nanodroplets, the interfaces of which are decorated with surfactant molecules that promote local perpendicular orientation of mesogens within the droplet. In the absence of surfactant, mesogens at the interface are all parallel to that interface. As the droplet is cooled, the mesogens undergo a transition from a disordered (isotropic) to an ordered (nematic or smectic) liquid-crystal phase. As this happens, mesogens within the droplet cause a transition of the surfactant at the interface, which forms new ordered nanophases with morphologies dependent on surfactant concentration. Such nanophases are reminiscent of those encountered in block copolymers, and include circular, striped and worm-like patterns.

Optical security device providing fingerprint and designed pattern indicator using fingerprint texture in liquid crystal

An optical security device providing the function of a fingerprint for authentication along with a designed pattern storage function has been proposed. The proposed device uses the random fingerprint texture in the chiral nematic phase of an ultraviolet-curable liquid crystal. Using photopolymerization along with a mask of the designed pattern, a unique pattern can be fixed in the shape of the designed pattern. The random patterns can be used as a fingerprint for such devices. This proposed device has the potential to be an optical security device and an authenticity or information indicator for the user.

Molecular-field-theory approach to the Landau theory of liquid crystals: Uniaxial and biaxial nematics

Nematic liquid crystal phase diagrams in temperature-biaxiality space are usually complex. We construct a Landau theory based on the analogous molecular-field theory for orthorhombic biaxial nematic fluids. A formal procedure yields coefficients (some of which, unusually, can be tensorial) in this Landau expansion, correctly predicts the complete set of invariants formed from the ordering tensors, and avoids ad hoc parametrization of the molecular biaxiality. By regularizing the Landau expansion to avoid unwanted order parameter divergences at low temperatures, we predict phase behavior over the whole range of biaxiality. The resulting phase diagrams have the same topology as those of molecular-field theory.

Full-field optical coherence tomography using nematic liquid-crystal phase shifter

We present a polarization Linnik interference microscope with a nematic liquid-crystal (NLC) phase shifter for full-field optical coherence tomography of high-quality images. The rotating half-wave plate in conventional achromatic phase shifters was replaced by three liquid-crystal (LC) half-wave plates for implementing three-step phase-shifting interferometry. Thus, the NLC device generates phase shifts quickly and has no vibrations. In addition, the phase shift can be set to an arbitrary value between 0 and 2π by altering the azimuth angles of the LC cells. A tomographic image is retrieved from three sequential phase-shifted interferograms by using a three-step algorithm. The experimental results confirm the feasibility of the proposed technology.

Helically π-Stacked Thiophene-Based Copolymers with Circularly Polarized Fluorescence: High Dissymmetry Factors Enhanced by Self-Ordering in Chiral Nematic Liquid Crystal Phase

Novel derivatives of polythiophenes and their phenylene copolymers were synthesized by introducing chiral alkoxy carbonyl substituents into their side chains. Most of these polymers showed enantiotropic main-chain liquid crystallinity at high temperatures and across a wide range of elevated temperatures. They exhibited fluorescence that ranged in color from blue to orange in chloroform solutions and from blue to red in films. The bisignate Cotton effect was observed in the π–π* transition region of the circular dichroism (CD) spectra of the polymers consisting of three aromatic rings in the repeating unit, which was attributed to the formation of a polymer assembly with an interchain helically π-stacked structure. The dependence of UV–vis absorption and CD spectra on the concentration and temperature of the solution indicated that the polymer assembly exists, even in dilute concentration at room temperature, but it dissociated into single polymers at high temperatures. Additionally, the polymer films exhibited an enhanced Cotton effect caused by the strengthening of the helical π-stacking in the polymer assembly. Both the polymer solutions and films generated circularly polarized fluorescence with values for gem, the dissymmetry factor, on the order of 10–3 and 10–2, respectively. Values for gem as high as 10–1 were obtained by annealing the polymer films at temperatures corresponding to the liquid crystalline region and were due to the self-ordering of their chiral nematic phases. Furthermore, a mixture of red, green, and blue fluorescent polymers generated a unique, circularly polarized white luminescence not only in solution but also in the cast film prepared by dispersing the mixture in an excess of polystyrene.

Twist viscosities and flow alignment of biaxial nematic liquid crystal phases of a soft ellipsoid-string fluid studied by molecular dynamics simulation

We have calculated the twist viscosity and the alignment angle between the director and the stream lines in shear flow of a liquid crystal model system, which forms biaxial nematic liquid crystals, as functions of the density, from the Green-Kubo relations by equilibrium molecular dynamics simulation and by a nonequilibrium molecular dynamics algorithm, where a torque conjugate to the director angular velocity is applied to rotate the director. The model system consists of a soft ellipsoid-string fluid where the ellipsoids interact according a repulsive version of the Gay-Berne potential. Four different length-to-width-to-breadth ratios have been studied. On compression, this system forms discotic or calamitic uniaxial nematic phases depending on the dimensions of the molecules, and on further compression a biaxial nematic phase is formed. In the uniaxial nematic phase there is one twist viscosity and one alignment angle. In the biaxial nematic phase there are three twist viscosities and three alignment angles corresponding to the rotation around the various directors and the different alignments of the directors relative to the stream lines, respectively. It is found that the smallest twist viscosity arises by rotation around the director formed by the long axes, the second smallest one arises by rotation around the director formed by the normals of the broadsides, and the largest one by rotation around the remaining director. The first twist viscosity is rather independent of the density whereas the last two ones increase strongly with density. One finds that there is one stable director alignment relative to the streamlines, namely where the director formed by the long axes is almost parallel to the stream lines and where the director formed by the normals of the broadsides is almost parallel to the shear plane. The relative magnitudes of the components of the twist viscosities span a fairly wide interval so this model should be useful for parameterisation experimental data.

Self-Assembly of Bifunctional Patchy Particles with Anisotropic Shape into Polymers Chains: Theory, Simulations, and Experiments

Concentrated solutions of short blunt-ended DNA duplexes, as short as 6 base pairs, are known to order into the nematic liquid crystal phases. This self-assembly is due to the stacking interactions between duplex terminals that promotes their aggregation into polydisperse chains with a significant persistence length. Experiments show that liquid crystal phases form above a critical volume fraction depending on the duplex length. We introduce and investigate via numerical simulations, a coarse-grained model of DNA double-helical duplexes. Each duplex is represented as an hard quasi-cylinder whose bases are decorated with two identical reactive sites. The stacking interaction between terminal sites is modeled via a short-range square-well potential. We compare the numerical results with predictions based on a free energy functional and find satisfactory quantitative matching of the isotropic–nematic phase boundary and of the system structure. Comparison of numerical and theoretical results with experimental findings confirm that the DNA duplex self-assembly can be properly modeled via equilibrium polymerization of cylindrical particles. This insight enables us to estimate the stacking energy.

Short-range correlations seen in the nematic phase of bent-core liquid crystals by dielectric and electro-optic studies

Three bent-core nematic liquid crystals having the same core but with different terminal groups, short (C4) and long (C7,C9) tails, are investigated by dielectric and electro-optic contrast spectroscopic techniques. C4 shows sign reversal in the dielectric anisotropy Δε' as a function of both temperature and frequency, whereas C9 shows only negative Δε' in the entire mesophasic region. The behavior of C7 is intermediate of the two. Results of a dielectric study show that both C7 and C9 exhibit strong short-range polar correlations normal to the director. The correlation lengths of these interactions are found to be similar to those from the x-ray scattering. An increased hindered rotation for C9 compared to C4 moves the dielectric dispersion for ε(|') to much lower frequencies, such that C9 shows only negative Δε' over the entire temperature range.

Photoinduced Processes in Some Mechanically Interlocked Supramolecules as Studied by Time-Resolved Electron Paramagnetic Resonance

Time-resolved electron paramagnetic resonance (TREPR) spectroscopy was used for studying photoinduced intramolecular electron transfer (ET) and energy transfer (EnT) processes in three mechanically interlocked molecules in which zinc(II)porphyrin (ZnP) and C60 fullerene moieties are arrayed around a central Cu(I) bisphenanthroline core used to assemble these donor–acceptor (D–A) systems. The specific molecules studied include a “long” (ZnP)2–Cu(I)(phen)2–C60 rotaxane as well as ZnP–Cu(I)(phen)2 and ZnP–Cu(I)(phen)2–C60 catenanes, embedded in different phases of nematic liquid crystal and frozen isotropic solvents. It was demonstrated that the routes and rates of the transfer processes in these supramolecules strongly depend on the characteristics of their microenvironment and the molecular entity which was selectively photoexcited. This is reflected by formation of distinct long-lived charge-separated species such as the radical ion pair (ZnP)2•+–Cu(I)(phen)2•– and the metal-to-ligand charge-separated state Cu(II)–(phen)2•– under the various experimental conditions. The results are discussed in terms of the correlation between the chemical structure, conformational mobility, and relaxation pathways of the photoexcited states in these mechanically interlocked systems. Results are compared with previously reported TREPR data on related interlocked D–A porphyrin/fullerene systems.

The emergence of memory in liquid crystals

The nematic phase of liquid crystals (LC), used in most LC display applications, is a fluid state formed by orientationally ordered molecules. The direction of their alignment, and hence the overall optical response of the material, is easily modified by the application of an electric field and elastically relaxes back to a well-defined off-state when the field is removed. It has been recently shown that hybrid materials formed by nematic LCs incorporated in complex micro-structured porous matrices are often capable of indefinitely retaining the alignment direction imposed by an electric field. Such multistability is ultimately due to the interactions of the porous material with the lines of topological defects that develop within the confined nematic. Controlling the defect lines and their interactions is crucial to the design of materials whose optical properties are electrically driven but spontaneously preserved.

Helical phase of chiral nematic liquid crystals as the Bianchi VII0group manifold

We show that the optical structure of the helical phase of a chiral nematic is naturally associated with the Bianchi VII(0) group manifold, of which we give a full account. The Joets-Ribotta metric governing propagation of the extraordinary rays is invariant under the simply transitive action of the universal cover E(2) of the three-dimensional Euclidean group of two dimensions. Thus extraordinary light rays are geodesics of a left-invariant metric on this Bianchi type VII(0) group. We are able to solve, by separation of variables, both the wave equation and the Hamilton-Jacobi equation for this metric. The former reduces to Mathieu's equation, and the latter to the quadrantal pendulum equation. We discuss Maxwell's equations for uniaxial optical materials where the configuration is invariant under a group action and develop a formalism to take advantage of these symmetries. The material is not assumed to be impedance matched, thus going beyond the usual scope of transformation optics. We show that for a chiral nematic in its helical phase Maxwell's equations reduce to a generalized Mathieu equation. Our results may also be relevant to helical phases of some magnetic materials and to light propagation in certain cosmological models.

Hydration-Responsive Folding and Unfolding in Graphene Oxide Liquid Crystal Phases

Graphene oxide is promising as a plate-like giant molecular building block for the assembly of new carbon materials. Its water dispersibility, liquid crystallinity, and ease of reduction offer advantages over other carbon precursors if its fundamental assembly rules can be identified. This article shows that graphene oxide sheets of known lateral dimension form nematic liquid crystal phases with transition points in agreement with the Onsager hard-plate theory. The liquid crystal phases can be systematically ordered into defined supramolecular patterns using surface anchoring, complex fluid flow, and microconfinement. Graphene oxide is seen to exhibit homeotropic surface anchoring at interfaces driven by excluded volume entropy and by adsorption enthalpy associated with its partially hydrophobic basal planes. Surprisingly, some of the surface-ordered graphene oxide phases dry into graphene oxide solids that undergo a dramatic anisotropic swelling upon rehydration to recover their initial size and shape. This behavior is shown to be a unique hydration-responsive folding and unfolding transition. During drying, surface tension forces acting parallel to the layer planes cause a buckling instability that stores elastic energy in accordion-folded structures in the dry solid. Subsequent water infiltration reduces interlayer frictional forces and triggers release of the stored elastic energy in the form of dramatic unidirectional expansion. We explain the folding/unfolding phenomena by quantitative nanomechanics and introduce the potential of liquid crystal-derived graphene oxide phases as new stimuli-response materials.

Spectroscopic and morphological investigation of conjugated photopolymerisable quinquethiophene liquid crystals

3′-methyl-(5,5′′-bis[3-ethyl-3-(6-phenyl-hexyloxymethyl)-oxetane])-2,2′:5′,2′′-terthiophene (5T(Me)Ox) is a solution processable small molecule semiconductor displaying smectic-C and nematic liquid crystal phases. The pendant oxetane group can be polymerized in situ in the presence of a suitable photoacid at concentrations ≥1% by weight. Spin-coated films of pure 5T(Me)Ox and 5T(Me)Ox doped with the soluble photoacid were characterized by absorption and photoluminescent spectroscopy. Thick pristine films showed absorption and emission from a crystalline phase. Thin monolayer (<5 nm) films, as well as thicker photoacid doped films, instead showed absorption from an H-aggregate phase and emission from an excimer. Optical microscopy showed a significant change in film structure upon addition of the photoacid; large and well-orientated crystals being replaced by much smaller domains which appear to vary in thickness. Grazing Incidence Wide Angle X-Ray Scattering (GIWAXS) was used to characterize the packing and orientation of molecules in the crystalline and doped samples. The results are consistent with the photoacid doped samples forming layers of H-aggregate phase monolayer sheets parallel to the substrate where the photoacid inhibits the transition into the three-dimensionally ordered crystalline phase. Field-effect transistors and light emitting diodes were constructed incorporating 5T(Me)Ox as the active layer. Pure 5T(Me)Ox field-effect transistors showed good, p-type device characteristics, but the morphological changes upon doping result in a loss of transistor action. In the diodes, curing through melting and exposure to UV light followed by photoacid removal resulted in an increase in current density but a decrease in light emission. These results indicate that the presence of the photoacid (≥1% by weight) can have a dramatic effect on the structure, morphology and device performance of ordered, photopatternable materials for organic electronics.

Heat transport in polymer-dispersed liquid crystals under electric field

The concepts of effective thermal conductivity and interfacial thermal contact resistance in composite media are applied to study heat transport in polymer-dispersed liquid crystals (PDLC). In these systems, the thermal properties of liquid crystal inclusions are changed by an imposed electric field. The photopyroelectric (PPE) technique with a cell allowing the application of an electric field to the sample is used to measure the thermal parameters. A model based on effective medium approximation is used to assess the impact of interfaces on the flow of heat through the determination of the Kapitza radius. It was found that the effect of interfaces becomes dominant compared to the volume conduction of the droplet when the liquid crystal (LC) droplet radius becomes smaller than 1 micron. The comparison of the thermal behavior of LC in the droplets with that of bulk liquid crystal allowed to evaluate the effect of confinement on the LC nematic phase.

Highly birefringent nematic mixtures at room temperature for microwave applications

We present results on how the dielectric anisotropy in the low frequency region up to 1 GHz and the birefringence of the nematic liquid crystal (LC) phase at optical wavelength (589 nm) influences the performance of LC mixtures at microwave frequencies. For this, we prepared a wide range of mixtures being nematic at room temperature and containing different classes of promising compounds. Their quasistatic and frequency depended dielectric properties, their birefringence and the impact of those properties on their microwave behavior were investigated. The measurements were done using the cavity perturbation method at 30 and 38 GHz, respectively, in the temperature interval of -20°C and 135°C.

Steady State–Hopf Mode Interactions at the Onset of Electroconvection in the Nematic Liquid Crystal Phase V

We report on a new mode interaction found in electroconvection experiments on the nematic liquid crystal mixture Phase V in planar geometry. The mode interaction (codimension two) point occurs at a critical value of the frequency of the driving AC voltage. For frequencies below this value the primary pattern-forming instability at the onset voltage is an oblique stationary instability involving oblique rolls, and above this value it is an oscillatory instability giving rise to normal traveling rolls (oriented perpendicular to and traveling in the director direction). The transition has been confirmed by measuring the roll angle and the dominant frequency of the time series, as both quantities exhibit a discontinuous jump across zero when the AC frequency is varied near threshold. The globally coupled system of Ginzburg–Landau equations that qualitatively describe this mode interaction is constructed, and the resulting normal form, in which slow spatial variations of the mode amplitudes are ignored, is analyzed. This analysis shows that the Ginzburg–Landau system provides the adequate theoretical description for the experimentally observed phenomenon. The experimentally observed patterns at and higher above the onset allow us to narrow down the range of the parameters in the normal form.