Open Access Kent State (OAKS)

We have developed a fully nonlocal model to describe the dynamic behavior of nematic liquid-crystal elastomers. The free energy, incorporating both elastic and nematic contributions, is a function of the material displacement vector and the orientational order parameter tensor. The free energy cost of spatial variations of these order parameters is taken into account through nonlocal interactions rather than through the use of gradient expansions. We also give an expression for the Rayleigh dissipation function. The equations of motion for displacement and orientational order are obtained from the free energy and the dissipation function by the use of a Lagrangian approach. We examine the free energy and the equations of motion in the limit of long-wavelength and small-amplitude variations of the displacement and the orientational order parameter. We compare our results with those in the literature. If the scalar order parameter is held fixed, we recover the usual viscoelastic theory for nematic liquid crystals.

Molecular shape is an important factor in determining the material properties of thermotropic liquid crystals (LCs). We synthesized and investigated several LC compounds formed by asymmetrically bent molecules with a rigid four-ring core in the shape of the letter 'L'. We measured the temperature dependencies of dielectric permittivities, birefringence, splay K-1 and bend K-3 elastic constants, splay viscosity eta(splay) and flow viscosities eta(parallel to) and eta(perpendicular to). The bend-splay anisotropy delta K-31 - K-3 - K-1 is negative, similar to the case of nematic LCs formed by symmetrically bent molecules of V-shape. The dielectric anisotropy Delta epsilon and birefringence are positive in the entire nematic range. The splay viscosity eta(splay) and the flow viscosities eta(parallel to) and eta(perpendicular to) are smaller than the viscosities measured for the symmetric V-shaped bent-core materials at similar temperatures. The ratio Gamma = eta(splay)/eta(parallel to,perpendicular to) is in the range 5-4 that is typical for rod-like LCs. The reported L-shaped bent-core nematic LCs combine the useful features of bent-core LCs (such as a negative delta K-31, suitable for formulation of broad-range blue phases) with the relatively low viscosities, a property typical for rod-like LCs and beneficial for electro-optic switching applications.

Liquid crystals are a class of industrially important materials whose optical properties make them useful particularly in display technology. Optical imaging of these materials provides information about their structure and physical properties. Coherent anti-Stokes Raman scattering (CARS) microscopy is used to provide three-dimensional chemical maps of liquid crystalline samples without the use of external labels. CARS is an optical imaging technique that derives contrast from Raman-active molecular vibrations in the sample. Compared to many other three-dimensional imaging techniques, CARS offers more rapid chemical characterization without the use of external dyes or contrast agents. The use of CARS to image chemical and orientational order in liquid crystals is demonstrated using several examples, and the limitations and benefits are discussed.

Deuteron quadrupole-perturbed NMR is used to study the perturbation of orientational order in a smectic-A liquid crystal (octylcyanobiphenyl or 8CB) caused by photoinduced trans-to-cis isomerization of a photosensitive dopant (diheptylazobenzene or 7AB). The time and temperature dependences of the orientational order were independently studied for 8CB, 7AB, and their mixtures. Upon UV irradiation that causes trans-to-cis isomerization of 7AB, the orientational order parameter of the smectic-A phase is reduced. Relaxation in the dark exponentially restores the equilibrium value of the order parameter. The characteristic time for this process closely matches the lifetimes of the 7AB excited state. While in the 8CB smectic-A matrix, the cis-isomerized 7AB molecules retain a uniaxial orientational order with the director oriented along the normal to the smectic layers. The highly bent 7AB cis molecules act as a disorienting factor, decreasing the orientational order in the layers and causing a small increase in layer spacing. This disorder-induced increase in layer spacing is much smaller than the actual increase as observed by in situ x-ray experiments on UV-irradiated mixtures of 8CB:7AB. Concomitant with the experimental observation that only a fraction of 7AB molecules are converted to the cis state, this work provides indirect evidence for a nanophase segregation with the 7AB cis-isomers arranged within the interlayer space, thus significantly increasing the smectic layer spacing.

The distance of closest approach of hard particles is a key parameter of their interaction and plays an important role in the resulting phase behavior. For nonspherical particles, the distance of closest approach depends on orientation, and its calculation is surprisingly difficult. Although overlap criteria have been developed for use in computer simulations [ Vieillard-Baron J. Chem. Phys. 56 4729 (1972); Perram and Wertheim J. Comput. Phys. 58 409 (1985)], no analytic solutions have been obtained for the distance of closest approach of ellipsoids in three dimensions, or, until now, for ellipses in two dimensions. We have derived an analytic expression for the distance of closest approach of the centers of two arbitrary hard ellipses as a function of their orientation relative to the line joining their centers. We describe our method for solving this problem, illustrate our result, and discuss its usefulness in modeling and simulating systems of anisometric particles such as liquid crystals.

The distance of closest approach of hard particles is a key parameter of their interaction and plays an important role in the resulting phase behavior. For nonspherical particles, the distance of closest approach depends on orientation, and its calculation is surprisingly difficult. Although overlap criteria have been developed for use in computer simulations [ Vieillard-Baron J. Chem. Phys. 56 4729 (1972); Perram and Wertheim J. Comput. Phys. 58 409 (1985)], no analytic solutions have been obtained for the distance of closest approach of ellipsoids in three dimensions, or, until now, for ellipses in two dimensions. We have derived an analytic expression for the distance of closest approach of the centers of two arbitrary hard ellipses as a function of their orientation relative to the line joining their centers. We describe our method for solving this problem, illustrate our result, and discuss its usefulness in modeling and simulating systems of anisometric particles such as liquid crystals.

A two-dimensional (2D) solid lacks long-range positional order and is diffusive by means of the cooperative motion of particles. We find from molecular dynamics simulations of hard discs that 2D colloids in solid and hexatic phases show seemingly Fickian but strongly heterogeneous dynamics. Beyond translational relaxation time, the mean-square displacement is linear with time, t, implying that discs would undergo Brownian diffusion and the self-part of the van Hove correlation function [G(s)(r, t)] might be Gaussian. But dynamics is still heterogeneous and G(s)(r, t) is exponential at large r and oscillatory with multiple peaks at intermediate length. We attribute the existence of several such peaks to the observation that there are several clusters of discs with discretized mobility. The cluster of marginally mobile discs grows with time and begins to percolate around translational relaxation time while clusters of fast discs emerge in the middle of the marginally mobile cluster.

We propose lyotropic chromonic liquid crystals (LCLCs) as a distinct class of materials for organic electronics. In water, the chromonic molecules stack on top of each other into elongated aggregates that form orientationally ordered phases. The aligned aggregated structure is preserved when the material is deposited onto a substrate and dried. The dried LCLC films show a strongly anisotropic electric conductivity of semiconductor type. The field-effect carrier mobility measured along the molecular aggregates in unoptimized films of LCLC V20 is 0.03 cm(2) V-1 s(-1). Easy processibility, low cost, and high mobility demonstrate the potential of LCLCs for microelectronic applications. (C) 2010 American Institute of Physics.

We study optical, structural, and surface anchoring properties of thermotropic nematic bent-core material A131. The focus is on the features associated with orientational order as the material has been reported to exhibit not only the usual uniaxial nematic but also the biaxial nematic phase. We demonstrate that A131 experiences a surface anchoring transition from a perpendicular to tilted alignment when the temperature decreases. The features of the tilted state are consistent with surface-induced birefringence associated with smectic layering near the surface and a molecular tilt that changes along the normal to the substrates. The surface-induced birefringence is reduced to zero by a modest electric field that establishes a uniform uniaxial nematic state. Both refractive and absorptive optical properties of A131 are consistent with the uniaxial order. We found no evidence of the “polycrystalline” biaxial behavior in the cells placed in crossed electric and magnetic fields. We observe stable topological point defects (boojums and hedgehogs) and nonsingular “escaped” disclinations pertinent only to the uniaxial order. Finally, freely suspended films of A131 show uniaxial nematic and smectic textures; a decrease in the film thickness expands the temperature range of stability of smectic textures, supporting the idea of surface-induced smectic layering. Our conclusion is that A131 features only a uniaxial nematic phase and that the apparent biaxiality is caused by subtle surface effects rather than by the bulk biaxial phase.

We develop a Landau theory for bend flexoelectricity in liquid crystals of bent-core molecules. In the nematic phase of the model, the bend flexoelectric coefficient increases as we reduce the temperature toward the nematic to polar phase transition. At this critical point, there is a second-order transition from high-temperature uniform nematic phase to low-temperature nonuniform polar phase composed of twist-bend or splay-bend deformations. To test the predictions of Landau theory, we perform Monte Carlo simulations to find the director and polarization configurations as functions of temperature, applied electric field, and interaction parameters.