Impact of spherical nanoparticles on nematic order parameters.

We study experimentally the impact of spherical nanoparticles on the orientational order parameters of a host nematic liquid crystal. We use spherical core-shell quantum dots that are surface functionalized to promote homeotropic anchoring on their interface with the liquid crystal host. We show experimentally that the orientational order may be strongly affected by the presence of spherical nanoparticles even at low concentrations. The orientational order of the composite system is probed by means of polarized micro-Raman spectroscopy and by optical birefringence measurements as function of temperature and concentration. Our data show that the orientational order depends on the concentration in a nonlinear way, and the existence of a crossover concentration χ_{c}≈0.004pw. It separates two different regimes exhibiting pure-liquid crystal like (χ<χ_{c}) and distorted-nematic ordering (χ>χ_{c}), respectively. In the latter phase the degree of ordering is lower with respect to the pure-liquid crystal nematic phase.

Analysis of Warburg's impedance and its equivalent electric circuits.

The derivation of Warburg's impedance is revisited and critically analyzed. We show that the original derivation where the electric current is assumed to be due only to the diffusion of ions, as proposed by Warburg, raises some fundamental questions. The roles of the drift current, in the absence of which the equilibrium is never reached in the dc case, and of the displacement current, which is important even in the low frequency region where the Warburg's impedance appears, are discussed. Finally, the utility of models based on equivalent electric circuits, ladder networks, or transmission lines in the analysis of impedance spectroscopy data is investigated.

Role of the displacement current on Warburg-type behavior.

We investigate the role of the displacement current in the analysis of the electric response of an electrolytic cell to an external stimulus. We show that several models proposed to interpret the spectra deduced by means of the impedance spectroscopy technique are questionable. In particular, we demonstrate that even in the frequency range below the Debye frequency the role of the displacement current is fundamental, and its omission leads to incorrect results for the impedance of the cell. In our analysis, the boundary conditions on the bulk current density are of Nernstian and of Ohmic type. The analysis is limited to a fully dissociated electrolyte, and for only one type of mobile ions, as discussed in several papers devoted to the subject. Particular attention is given to the spatial dependence of the current density. We show that Warburg-like behavior is never predicted in the framework of the Poisson-Nernst-Planck model, if the electric impedance of the cell is correctly evaluated. From this conclusion, valid for media with only one type of mobile ions, it follows that if Warburg-like behavior is experimentally observed the theoretical interpretation is still an open problem, and its origin is probably related to the boundary conditions.

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.

Comment on "Modeling of electrode polarization for electrolytic cells with a limited ionic adsorption".

Recently, Sawada [Phys. Rev. E 88, 032406 (2013)] proposed a model to take into account the dielectric dispersion of ionic origin in a weak electrolyte cell. We first show that the model is based on questionable assumptions. Next, we point out an error in the author's calculation of the current in the external circuit. Finally, we demonstrate why some criticism on recent papers is irrelevant.

Independence of the effective dielectric constant of an electrolytic solution on the ionic distribution in the linear Poisson-Nernst-Planck model.

We consider the influence of the spatial dependence of the ions distribution on the effective dielectric constant of an electrolytic solution. We show that in the linear version of the Poisson-Nernst-Planck model, the effective dielectric constant of the solution has to be considered independent of any ionic distribution induced by the external field. This result follows from the fact that, in the linear approximation of the Poisson-Nernst-Planck model, the redistribution of the ions in the solvent due to the external field gives rise to a variation of the dielectric constant that is of the first order in the effective potential, and therefore it has to be neglected in the Poisson's equation that relates the actual electric potential across the electrolytic cell to the bulk density of ions. The analysis is performed in the case where the electrodes are perfectly blocking and the adsorption at the electrodes is negligible, and in the absence of any ion dissociation-recombination effect.

Cholesteric pitch transitions induced by mechanical strain.

We investigate thickness and surface anchoring strength influence on pitch transitions in a planar cholesteric liquid crystal layer. The cholesteric-nematic transition is also investigated. We assume planar boundary conditions, with strong anchoring strength at one interface and weak anchoring strength at the other. The surface anchoring energy we consider to describe the deviation of the surface twist angle from the easy axis induced by a bulk deformation is a parabolic potential or Rapini and Papoular periodic potential, respectively. We show that under strain, all pitch transitions take place at a critical thickness that is equal to the quarter of the natural cholesteric pitch. The latter result does not depend on the anchoring strength, the particular surface potential, or material properties. The twist angle on the limiting surface characterized by weak anchoring varies with strain either by slipping and or in a discontinuous manner according to the thickness of the sample. The position of the bifurcation point depends only on the ratio of the extrapolation length over the layer thickness, but its value is model dependent. Multistability and multiplicity of the transition are discussed.

Comparison of two generation-recombination terms in the Poisson-Nernst-Planck model.

Two phenomenological forms proposed to take into account the generation-recombination phenomenon of ions are investigated. The first form models the phenomenon as a chemical reaction, containing two coefficients describing the dissociation of neutral particles in ions, and the recombination of ions to give neutral particles. The second form is based on the assumption that in thermodynamical equilibrium, a well-defined density of ions is stable. Any deviation from the equilibrium density gives rise to a source term proportional to the deviation, whose phenomenological coefficient plays the role of a life time. The analysis is performed by evaluating the electrical response of an electrolytic cell to an external stimulus for both forms. For simplicity we assume that the electrodes are blocking, that there is only a group of negative and positive ions, and that the negative ions are immobile. For the second form, two cases are considered: (i) the generation-recombination phenomenon is due to an intrinsic mechanism, and (ii) the production of ions is triggered by an external source of energy, as in a solar cell. We show that the predictions of the two models are different at the impedance as well as at the admittance level. In particular, the first model predicts the existence of two plateaux for the real part of the impedance, whereas the second one predicts just one. It follows that impedance spectroscopy measurements could give information on the model valid for the generation-recombination of ions.

Electrical response of a medium containing dissociable impurities.

The effect of the generation-recombination phenomenon on the electrical impedance of an electrolytic cell is investigated. We show that this phenomenon could be responsible for the appearance of a plateau in the real part of the impedance of the cell. The possibility to observe the plateau, arising from the generation-recombination phenomenon, is discussed in relation to the values of the association-dissociation coefficients. The analysis is done by assuming that the generation-recombination phenomenon can be described as a chemical reaction of first order, that the sample is in the shape of a slab, and that the electrodes of the cell are perfectly blocking. To simplify the analysis, the case where only one type of ions can move is considered. The extension of the results to the more general case, in which both types of ions are mobile, is also discussed.

Complex dielectric constant of a nematic liquid crystal containing two types of ions: limit of validity of the superposition principle.

We investigate the influence of two groups of ions on the complex dielectric constant of a nematic liquid crystal limited by perfectly blocking electrodes. The analysis is performed by solving the equations of continuity for the two groups of cations and anions, and the equation of Poisson relating the actual electric field to the net density of charge. We consider a typical experiment of impedance spectroscopy, and evaluate the equivalent resistance and reactance of the cell, in the series representation, versus the frequency of the applied voltage to the cell. We show that the presence of two groups of ions gives rise to two plateaux in the spectrum of the resistance, similar to those related to the ambipolar and free diffusion in the case where there is only one type of ions, but for which the cations and anions have different diffusion coefficients. The correspondence between the usual ambipolar and free diffusion coefficients and those related to the presence of two groups of ions is discussed. The spectra of the real and imaginary parts of the complex dielectric constant are obtained, and their dependence on the bulk densities of the two types of ions is investigated. The nonvalidity of the superposition principle is discussed.

Models for ionic contribution to the complex dielectric constant of nematic liquid crystals.

We analyze the models that account the ionic contribution to the complex dielectric constant of a nematic liquid crystal. We compare the predictions of the model of [Sawada, Mol. Cryst. Liq. Cryst. Sci. Technol., Sect. A 318, 225 (1998)] based on the assumption that the electric field in the liquid coincides with the applied one, with the model of Macdonald where the electric field in the sample is determined in self-consistent manner by solving the equation of Poisson. We show that the model of Sawada , widely used to determine the bulk density of ions and their diffusion coefficient in liquid crystal cells, predicts a thickness dependence of the real and imaginary parts of the dielectric constant different from that predicted by the model of Macdonald. On the contrary, the predictions of the two models coincide for what concerns the frequency dependencies of the two components of the dielectric constant. By considering a typical case, we show that the numerical values of the ionic properties derived by means of the model of Sawada may differ even more than 1 order of magnitude by those predicted by the model of Macdonald. A rescaling procedure allowing to evaluate the bulk density of ions and the ionic diffusion coefficient determined by means of the model of Sawada in agreement with the one of Macdonald is proposed.

Stripe domains in a nearly homeotropic nematic liquid crystal: a bend escaped state at a nematic-smectic-A transition.

We report an observation and mechanism of spontaneous periodic modulations of the nematic director close to the temperature T(NA) of a nematic-to-smectic-A phase transition if the surface alignment slightly differs from a pure homeotropic one. Stripe domains appear in the nematic phase about one degree above T(NA) and persist into the Sm A phase. The instability of the homogeneous state with respect to stripe domains is shown to be related to a very large bend constant which is much larger than the twist and splay elastic constants. The instability mechanism consists of reduction of the highly energetic bend deformation, induced by small surface director tilts, at the expense of a spontaneous periodic splay-twist modulation. Using smallness of the twist-to-bend and splay-to-bend elastic constant ratios, the critical condition of the instability and the modulation period are found analytically. Both the experimentally obtained and theoretically predicted domain period scales very closely to a square root of the cell thickness.

Relaxation times of an electrolytic cell subject to an external electric field: role of ambipolar and free diffusion phenomena.

We evaluate the relaxation times for an electrolytic cell subject to a step-like external voltage, in the case in which the mobility of negative ions is different from that of positive ions. The electrodes of the cell, in the shape of a slab, are supposed to be perfectly blocking. The theoretical analysis is performed by assuming that the applied voltage is so small that the fundamental equations of the problem can be linearized. In this framework, the eigenvalues equations defining all relaxation times of the problem are deduced. In the numerical analysis, we solve the complete set of equations describing the time evolution of the system under the action of the external voltage. Two relaxation processes, connected with the ambipolar and free diffusion phenomena, are sufficient to describe the dynamics of the system, when the diffusion coefficients are of the same order of magnitude.

Evidence of the ambipolar diffusion in the impedance spectroscopy of an electrolytic cell.

We argue that the impedance spectroscopy of an electrolytic cell in the low-frequency range can give information on the ambipolar diffusion. Our analysis is based on a theoretical investigation of the real part of the electrical impedance of an electrolytic cell. When the mobility of the positive ions differs from that of the negative ions, a second plateau of the resistance of the cell, in series representation, is expected close to the dc limit of the applied voltage. The effective diffusion coefficient, related to the measured resistance of the cell, in the dc limit, coincides with the ambipolar diffusion coefficient. The associated relaxation time corresponds to the ambipolar diffusion, and it is proportional to the square of the thickness of the sample. In the high-frequency range, the relaxation time coincides with the Debye relaxation time, connected to the free diffusion coefficient, and it is independent of the thickness of the sample. Finally, we propose a method to calculate the diffusion coefficients of the individual ions from the impedance spectrum and we discuss the implications of ambipolar diffusion in impedance measurements and interpretation of experimental quantities.

Ionic contribution to the electric current in an electrolytic cell submitted to an external voltage.

The ionic contribution to the electrical current in an electrolytic cell submitted to an external voltage linearly increasing with the time is evaluated. The investigation is performed in the limit of small and large electric field, in which the density of ions depends on the actual electric field in the sample. In the analysis, it is assumed that the ionic separation induced by an external field can be described by a surface density of charge. We show that the ions are responsible for a peak in the current, followed by a delay in the application of the external voltage. From the analysis of the peak and its delay, it is possible to obtain information on the density of ions in thermodynamical equilibrium, and on the mobility of the ions in the considered liquid.

Substrate induced 1D tilt-modulated state in nematic monolayers.

Symmetry considerations yield the general form, up to second order terms, for the deformation elastic energy of a nematic monolayer, composed by symmetric achiral molecules, on a rigid planar substrate. The deformation energy contains an elastic contribution linear in the deformation tensor, whose elements are the spatial derivatives of the average molecular orientation. This linear Lifshitz-invariant-like term can be responsible for a ground state of the nematic monolayer periodically deformed if the relevant elastic constant is stiffer than a critical value. The wave-length of the modulation diverges at the transition threshold. We show that only large variations of the tilt angle form stable states. The effect of a destabilizing electric or magnetic field on the layer is to induce (i) the transition towards the tilt-modulated phase, while (ii) for higher enough values of the field the modulation is destroyed.

Optical and confocal microscopy observations of screw dislocations in smectic-A liquid crystals.

We present experimental evidence of the presence of isolated screw dislocations in smectic-A liquid crystals observed by polarizing microscopy. In a wedge-shaped homeotropic cell, the edge and screw dislocations interaction gives rise to a strong-enough optical contrast and makes visible their mutual intersections at temperatures close to the smectic-A to smectic-C phase transition temperature. The nature of the defects is confirmed by confocal microscopy observations. At large scale we observe a forest of screw dislocations, perpendicular to the smectic layers, across the thickness of the cell (end-on configuration). Their density varies between 10(9) and 10(12) m-2. In situ observations of dislocations under stress, in the optical microscope, provide quantitative information about the screw-edge dislocation interactions. The latter interaction is calculated in the unharmonic approximation and it gives rise to an observed yield stress.

Modulated structures in nematic monolayers formed by symmetric molecules.

An analysis based on symmetry yields a general form for the deformation elastic energy of a nematic monolayer, formed by achiral symmetric molecules, deposited on a solid substrate. Lifshitz-invariant-like terms in the energy, which originate from the substrate field, can induce a modulated-tilt state if the anchoring energy is sufficiently low. A way to enhance the symmetry breaking is to apply a destabilizing magnetic or electric field that serves to lower the anchoring energy. In the case of an initial state with homeotropic alignment, the phase diagram displays a cusp-shaped tilt-modulated state intervening between two uniform tilt states.

Spontaneous periodic distortions in nematic liquid crystals: dependence on the tilt angle.

The possibility of spontaneous periodic distortions, depending on the tilt angle in a nematic liquid crystal sample, is investigated by means of a general formulation of the stability problem. It is shown that due to the presence of a surfacelike term in the free-energy density, the uniform pattern can be destabilized, giving rise to a periodic distortion of the director. Our analysis establishes, in general terms, the conditions for the formation of stable periodic structures in nematic samples. In particular, we determine the wavelengths for which the periodic distortion exists by investigating its dependence on the tilt angle, characterizing the uniform pattern, and on the saddle-splay elastic constant. The effect considered in our paper is a finite size effect, related to the slab geometry of the nematic sample under consideration.

Modulated structures of flexoelectric origin in nematic liquid crystals.

A structural instability of flexoelectric origin is predicted in a homeotropic cell, of insulating nematic liquid crystal, by the action of an electric field applied in the direction of the initially nonperturbed nematic director. The instability gives rise to a two-dimensional periodic structure. The critical field to observe the predicted modulated structure as well as the wavelength at the threshold are evaluated. Both vary as the inverse square root of the cell thickness. The role of the dielectric anisotropy on the phenomenon is investigated. Our analysis is performed in the limit of weak anchoring energy strength, where the extrapolation length is large with respect to the thickness of the nematic sample.