Frequency-Dependent Dielectric Permittivity in Poisson-Nernst-Planck Model.

The approaches developed for studying the polarization of molecules and the dynamics of ions in dielectric materials are usually considered separately. The two effects are often believed to take place in different frequency ranges. The low frequency response is usually dominated by ionic migration, whereas the high frequency response is played by molecular polarization. The goal here is to clarify the interplay between free and bound charge densities and their influences on permittivity and impedance profiles by proposing a version of the Poisson-Nernst-Planck (PNP) model that allows to include the effect of a frequency-dependent (and thus not instantaneous) polarizability.

Surface and finite-size effects on N-Sm-A-Sm-C phase transitions in free-standing films.

The present study is devoted to the investigation of surface anchoring and finite-size effects on nematic-smectic-A-smectic-C (N-Sm-A-Sm-C) phase transitions in free-standing films. Using an extended version of the molecular theory for smectic-C liquid crystals, we analyze how surface anchoring and film thickness affect the thermal behavior of the order parameters in free-standing smectic films. In particular, we determine how the transition temperature depends on the surface ordering and film thickness. We show that the additional orientational order imposed by the surface anchoring may lead to a stabilization of order parameters in central layers, thus modifying the nature of the phase transitions. We compare our results with experimental findings for typical thermotropic compounds presenting a N-Sm-A-Sm-C phase sequence.

Coarse-grained model of the nematic twist-bend phase from a stable state elastic energy.

The twist-bend nematic (N_{TB}) phase is a doubly degenerated heliconical structure with nanometric pitch and spontaneous bend and twist deformations. It is favored by symmetry-breaking molecular structures, such as bent dimers and bent-core molecules, and it is currently one of the burgeoning fields of liquid-crystal research. Although tremendous advances have been reported in the past five years, especially in molecular synthesis, most of its potential applications are held back by the lack of a proper and definitive elastic model to describe its behavior under various situations such as confinement and applied field. In this work we use a recently proposed stable state elastic model and the fact that the mesophase behaves as a lamellar structure to propose a mesoscopic or coarse-grained model for the N_{TB} phase. By means of standard procedures used for smectic and cholesteric liquid crystals, we arrive at a closed-form energy for the phase and apply it to a few situations of interest. The predicted compressibility for several values of the cone angle and the critical field for field-induced deformation agree well with recent experimental data.

Extensions and solutions for nonlinear diffusion equations and random walks.

We investigate a connection between random walks and nonlinear diffusion equations within the framework proposed by Einstein to explain the Brownian motion. We show here how to properly modify that framework in order to handle different physical scenarios. We obtain solutions for nonlinear diffusion equations that emerge from the random walk approach and analyse possible connections with a generalized thermostatistics formalism. Finally, we conclude that fractal and fractional derivatives may emerge in the context of nonlinear diffusion equations, depending on the choice of distribution functions related to the spreading of systems.

Influence of boundary conditions on the order and defects of biaxial nematic droplets.

We employ Monte Carlo simulations to study the defects occurring in a nematic droplet formed by biaxial molecules. The simulations are carried out using a lattice model based on a dispersive orientational biaxial potential previously employed to establish the rich phase diagram of the system. The focus of the present investigation is on the molecular organization inside the droplet when bipolar and toroidal anchoring conditions at the surface are considered. In both cases, we describe how the defect structure arises in the system, and we analyze the behavior of the defect core region in connection with the elastic properties of the phase in a continuum theory perspective.

Reliability of Poisson-Nernst-Planck Anomalous Models for Impedance Spectroscopy.

We investigate possible connections between two different implementations of the Poisson-Nernst-Planck (PNP) anomalous models used to analyze the electrical response of electrolytic cells. One of them is built in the framework of the fractional calculus and considers integro-differential boundary conditions also formulated by using fractional derivatives; the other one is an extension of the standard PNP model presented by Barsoukov and Macdonald, which can also be related to equivalent circuits containing constant phase elements (CPEs). Both extensions may be related to an anomalous diffusion with subdiffusive characteristics through the electrical conductivity and are able to describe the experimental data presented here. Furthermore, we apply the Bayesian inversion method to extract the parameter of interest in the analytical formulas of impedance. To resolve the corresponding inverse problem, we use the delayed-rejection adaptive-Metropolis algorithm (DRAM) in the context of Markov-chain Monte Carlo (MCMC) algorithms to find the posterior distributions of the parameter and the corresponding confidence intervals.

Effect of dynamically changing the substrate's easy axis on the response time of nematic samples.

Recent discoveries of advanced photocontrolled materials have kindled a great deal of interest on their use as command surfaces that switch easy axis under light radiation. One noticeable point when using switchable surfaces on any application is how the dynamical process propagates to the bulk directors. In this paper, we theoretically study the effect of a relaxing easy axis over time on a nematic sample when finite anchoring energy and surface viscosity are included. We first consider the case where just one of the substrates decay over time in an initially distorted director organization. Next, we assume that both substrates can be switched simultaneously. From the calculated director we obtained the optical profile and finally the molecular response time of the material. The response time depends on both the materials and the surfaces properties including its decay time. Our results might be used for understanding and engineering liquid crystal displays and other electro-optical devices with photocontrolled alignment layers.

Surface induced twist in nematic and chiral nematic liquid crystals: stick-slip-like and constrained motion.

Surface driven pattern formation is an intriguing phenomenon in the liquid crystal field. Owing to its ability to transmit torque, one can generate different patterns by propagating distortions on the optical wavelength scale in the sample from the surface. Here, we theoretically investigate (from the elasticity point of view) twist deformations induced by a rotating easy axis at one surface, by considering the anchoring energy and surface viscosity of nematic and chiral nematic samples. The model is solved analytically in the limit of strong anchoring and numerically for a low anchoring strength situation. Such rotation could be induced, in principle, by light-controlling the orientation of an azobenzene monolayer coated at one of the glass substrates or by an in-plane rotating field. We discuss the role of the surface parameters and the different distortions, and calculate light transmission using the Jones method. Three different regimes are identified: free twist, stick-slip twist, and constrained twist. The results obtained here may be relevant for liquid crystal active waveplates and for determining surface viscosity and the azimuthal anchoring energy.

On the Defect Structure of Biaxial Nematic Droplets.

We present a detailed Monte Carlo study of the effects of molecular biaxiality on the defect created at the centre of a nematic droplet with radial anchoring at the surface. We have studied a lattice model based on a dispersive potential for biaxial mesogens [Luckhurst et al., Mol. Phys. 30, 1345 (1975)] to investigate how increasing the biaxiality influences the molecular organisation inside the confined system. The results are compared with those obtained from a continuum theory approach. We find from both approaches that the defect core size increases by increasing the molecular biaxiality, hinting at a non universal behaviour previously not reported.

Elastic anisotropy effects on the electrical responses of a thin sample of nematic liquid crystal.

The electrical responses of a nematic liquid crystal cell are investigated by means of the elastic continuum theory. The nematic medium is considered as a parallel circuit of a resistance and a capacitance and the electric current profile across the sample is determined as a function of the elastic constants. In the reorientation process of the nematic director, the resistance and capacitance of the sample are determined by taking into account the elastic anisotropy. A nonmonotonic profile for the current is observed in which a minimum value of the current may be used to estimate the elastic constants values. This scenario suggests a theoretical method to determine the values of the bulk elastic constants in a single planar aligned cell just by changing the direction of applied electrical field and measuring the resulting electrical current.

Ion Motion in Electrolytic Cells: Anomalous Diffusion Evidences.

In this study, we argue that ion motion in electrolytic cells containing Milli-Q water, weak electrolytes, or liquid crystals may exhibit unusual diffusive regimes that deviate from the expected behavior, leading the system to present an anomalous diffusion. Our arguments lie on the investigation of the electrical conductivity and its relationship with the mean square displacement, which may be used to characterize the ionic motion. In our analysis, the Poisson-Nernst-Planck diffusional model is used with extended boundary conditions to simulate the charge transfer, accumulation, and/or adsorption-desorption at the electrode surfaces.

Anomalous diffusion and transport in heterogeneous systems separated by a membrane.

Diffusion of particles in a heterogeneous system separated by a semipermeable membrane is investigated. The particle dynamics is governed by fractional diffusion equations in the bulk and by kinetic equations on the membrane, which characterizes an interface between two different media. The kinetic equations are solved by incorporating memory effects to account for anomalous diffusion and, consequently, non-Debye relaxations. A rich variety of behaviours for the particle distribution at the interface and in the bulk may be found, depending on the choice of characteristic times in the boundary conditions and on the fractional index of the modelling equations.

Elastic continuum theory: towards understanding of the twist-bend nematic phases.

The twist-bend nematic phase, N_{TB}, may be viewed as a heliconical molecular arrangement in which the director n precesses uniformly about an extra director field, t. It corresponds to a nematic ground state exhibiting nanoscale periodic modulation. To demonstrate the stability of this phase from the elastic point of view, a natural extension of the Frank elastic energy density is proposed. The elastic energy density is built in terms of the elements of symmetry of the new phase in which intervene the components of these director fields together with the usual Cartesian tensors. It is shown that the ground state corresponds to a deformed state for which K_{22}>K_{33}. In the framework of the model, the phase transition between the usual and the twist-bend nematic phase is of second order with a finite wave vector. The model does not require a negative K_{33} in agreement with recent experimental data that yield K_{33}>0. A threshold is predicted for the molecular twist power below which no transition to a twist-bend nematic may occur.

Nematic liquid crystals in planar and cylindrical hybrid cells: Role of elastic anisotropy on the director deformations.

Nematic samples filling a flat cell or the annular region between two concentric cylinders with hybrid anchoring conditions at the boundaries are investigated by setting up and minimizing their Frank elastic free energy. The coupling with the surfaces is taken to be strong on one side and weak on the other. The equations are numerically solved and the conditions for which the molecular organization inside the cell becomes uniform are analyzed. The classical calculation performed by G. Barbero and R. Barberi [J. Phys. 44, 609 (1983)] is reproduced and investigated from a different point of view, in order to compare the results of planar and cylindrical geometries. The results suggest that the cylindrical cell presents some unusual features deserving a more complete investigation. Although most part of the transitional phenomena are found for K(11)>K(33), a case not common for ordinary (lyotropic and thermotropic) liquid crystals, it is possible to find a completely uniform cell even for K(11)

Molecular organization of nematic liquid crystals between concentric cylinders: role of the elastic anisotropy.

The orientational order in a nematic liquid crystal sample confined to an annular region between two concentric cylinders is investigated by means of lattice Monte Carlo simulations. Strong anchoring and homeotropic orientations, parallel to the radial direction, are implemented at the confining surfaces. The elastic anisotropy is taken into account in the bulk interactions by using the pair potential introduced by Gruhn and Hess [T. Gruhn and S. Hess, Z. Naturforsch. A 51, 1 (1996)] and parametrized by Romano and Luckhurst [S. Romano, Int. J. Mod. Phys. B 12, 2305 (1998); Phys. Lett. A 302, 203 (2002); G. R. Luckhurst and S. Romano, Liq. Cryst. 26, 871 (1999)], i.e., the so-called GHRL potential. In the case of equal elastic constants, a small but appreciable deformation along the cylinder axis direction is observed, whereas when the values of K(11)/K(33) if K(22)=K(33) are low enough, all the spins in the bulk follow the orientation imposed by the surfaces. For larger values of K(11)/K(33), spontaneous deformations, perpendicular to the polar plane, increase significantly. Our findings indicate that the onset of these deformations also depends on the ratio K(22)/K(33) and on the radius of the cylindrical surfaces. Although expected from the elastic theory, no tangential component of the deformations was observed in the simulations for the set of parameters analyzed.

Surface induced phase separation and pattern formation at the isotropic interface in chiral nematic liquid crystals.

We study the pattern formation of a chiral nematic liquid crystal under a wetting transition. In the isotropic-liquid crystal transition, a surface-enhanced effect happens and a thin liquid crystal layer forms at the substrates of the cell. In this confined system, chirality, elastic anisotropy, surface anchoring, and wetting strength interplay. A striped pattern is formed due to the chiral nature of the material and the tilted anchoring at the isotropic boundary. As the wetting layer grows from cooling the sample, first the stripes rotate through a process where dislocation defects are formed. As the wetting layer grows further, the periodicity of the stripe structure changes, and finally a splitting of the stripes occurs. Because of the unique properties of this system, new insights about pitch-thickness ratio, interface anchoring, and elastic anisotropy effect are found. Since the anchoring at the isotropic boundary is weak, the critical ratio between the thickness of the wetting layer and the helical pitch is different from that reported in the literature. We also discover that the elastic anisotropy and elastic constant ratios play a critical role in stripe formation. Because of the similarity with biological fibrous composites (twisted plywood), our system may be used as a synthetic version to mimic the naturally occurring one. We carry out a simulation study to explain the experimental results.

Non-Debye relaxation in the dielectric response of nematic liquid crystals: surface and memory effects in the adsorption-desorption process of ionic impurities.

We demonstrate theoretically that the presence of ions in insulating materials such as nematic liquid crystals may be responsible for the dielectric spectroscopy behavior observed experimentally. It is shown that, at low frequencies, an essentially non-Debye relaxation process takes place due to surface effects. This is accomplished by investigating the effects of the adsorption-desorption process on the electrical response of an electrolytic cell when the generation and recombination of ions is present. The adsorption-desorption is governed by a non-usual kinetic equation in order to incorporate memory effects related to a non-Debye relaxation and the roughness of the surface. The analysis is carried out by searching for solutions to the drift-diffusion equation that satisfy the Poisson equation relating the effective electric field to the net charge density. We also discuss the effect of the mobility of the ions, i.e., situations with equal and different diffusion coefficients for positive and negative ions, on the impedance and obtain an exact expression for the admittance. The model is compared with experimental results measured for the impedance of a nematic liquid crystal sample and a very good agreement is obtained.

Computer simulations of the ordering in a hybrid cylindrical film of nematic liquid crystals.

We present an investigation of the ordering in a nematic liquid-crystal film confined between two cylindrical surfaces with antagonistic (radial and planar) anchoring alignments. A Monte Carlo study of a Lebwohl-Lasher model with suitable boundary conditions has been performed to calculate the ordering and the molecular organization for different film thicknesses. The simulation results are compared with some theoretical predictions obtained with the elastic continuum approach. The agreement between theory and simulation is improved as the thickness decreases.

Anomalous diffusion and memory effects on the impedance spectroscopy for finite-length situations.

The contribution of ions to the electrical impedance of an electrolytic cell limited by perfect blocking electrodes is determined by considering the role of the anomalous diffusion process and memory effects. Analytical solutions for fractional diffusion equations together with Poisson's equation relating the effective electric field to the net charge density are found. This procedure allows the construction of general expressions for the electrochemical impedance satisfying the Kramers-Kronig relations when the diffusion of ions in the cell is characterized by the usual, as well as by anomalous, behavior.

Anomalous diffusion governed by a fractional diffusion equation and the electrical response of an electrolytic cell.

The electrical response of an electrolytic cell in which the diffusion of mobile ions in the bulk is governed by a fractional diffusion equation of distributed order is analyzed. The boundary conditions at the electrodes limiting the sample are described by an integro-differential equation governing the kinetic at the interface. The analysis is carried out by supposing that the positive and negative ions have the same mobility and that the electric potential profile across the sample satisfies the Poisson's equation. The results cover a rich variety of scenarios, including the ones connected to anomalous diffusion.