Tilted smectic layers of a liquid crystal between homeotropically treated plates

We investigated SmC^* films sandwiched between silane coated glass plates and observed formation of textures exhibiting a uniform tilt of the smectic layers with respect to the boundary plates. The layer tilt angle increases from zero to as the sample is cooled from the smectic A phase to room temperature. These films show linear electro-optical effects because the permanent polarization can be aligned so that it has a component parallel to the applied field without changing the layer structure. Our analysis indicates that mainly two effects determine the layer tilt. On the one hand, the surface tension tends to minimise the layer tilt. On the other hand, the surface energy promotes the director to be normal to the boundary plates. Received 17 July 1998     

Electric-field-induced chirality flipping in smectic liquid crystals: the role of anisotropic viscosity

We demonstrate the homogeneous and permanent reversal of the chirality of a condensed phase by an applied electric field. Tilted chiral smectic layers exhibit a coupled polarization density and molecular orientation fields which reorient about the layer normal as couple of fixed handedness in response to small applied electric fields. Experiments on some bent-core smectics show that above a threshold field the induced rotation can occur instead about the molecular long axis and that, as a result, the handedness of the phase can be flipped. The effect is quantitatively described by a nonequilibrium dissipative model of chiral smectic dynamics with anisotropic rotational viscosities.     

Effect of electric field on the rheology of ferroelectric liquid crystal MORA-8

Effects of electric field on the rheology, electrorheological effects, are investigated on ferroelectric smectic C* phase of 4-(6-methyl)octyl-resorcylidene-4′-octylaniline (MORA-8). When an electric field is applied in smectic C* phase, an increase of the shear stress is observed with its behavior depending on the shear rates; at higher shear rates the shear stress increases monotonously with the electric field strength, but at lower shear rates the shear stress increases monotonously until about 2 kV mm⁻¹, but above this field it discontinuously decreases to lower values, which is followed by an increase at higher electric fields. In close vicinity of the smectic C* to isotropic phase transition point, a field induced decrease of the shear stress is observed. These ER behaviors are discussed on the basis of the field induced orientational changes of the smectic layer and the director and a possible field induced structural change.     

Deformation of cholesteric elastomers by uniaxial stress along the helix axis

The deformation of cholesteric elastomers by mechanical stress applied parallel to the helix axis is studied by calculation of the free-energy density. The Frank-elasticity contribution is taken into account. A chiral solvent, present at cross-linking time, is in general considered to be replaced after cross-linking by a solvent with different chirality. Two special cases considered are zero and unchanged solvent chirality, the first known as that of imprinted cholesteric elastomers, the latter equivalent to intrinsic cholesteric elastomers with chemically attached chiral groups. Depending on material parameters and imposed strain, the director can show a tilt towards the helix axis up to the maximum tilt, corresponding to a nematic state. In case of intrinsic elastomers with low conformation anisotropy, direct transitions from untilted to nematic states can be induced by straining. The helix structure of the director field is coarsened with an average wave number different to that of the information inscribed in the network at cross-linking time, if this lowers the average free-energy density. Switching between different states can be achieved with electric fields of reasonable values applied parallel to the helix axis. Spectra of the reflection of polarized light are calculated.     

The effects of molecular shape and quadrupole moment on tilted smectic phase formation

Results are presented from constant NPT Monte Carlo simulations of two systems based on the biaxial internally rotated Gay-Berne (IRGB) potential. First, the effect of increasing molecular elongation is considered, and it is shown that a change in aspect ratio from 3:1 to 4:1 leads to nematic and tilted smectic J phases being replaced by smectic A and tilted smectic G phases, respectively. Second, the effect of a longitudinal electric quadrupole on the phase behaviour of the IRGB model is examined. The presence of a moderate quadrupole moment results in the smectic G phase being replaced by a smectic J; the onset pressure of the smectic J increases monotonically as the quadrupole moment is increased, although the integrity of the tilted layers improves. In addition, the region of smectic A stability is found to persist for moderate quadrupole moment values. For the largest quadrupole moment considered, domains comprising poorly defined, tilted layers are formed but fail to develop into coherent smectic structures. This observation is ascribed to the competition between the unique tilt direction favoured by the biaxial IRGB potential and the random tilt direction of the uniaxial quadrupole-quadrupole interactions.     

Synchrotron x-ray study of the smectic layer directional instability

We have investigated the phenomenon of field-induced smectic layer instability, as monitored by synchrotron x-ray scattering. This instability means that, upon application of time-asymmetric electric fields to chiral smectics, the layer direction seems to "rotate" locally around an axis given by the direction of the applied field. For moderate values of field amplitude and asymmetry, domains with a favored layer inclination grow at the expense of unfavored ones, while larger fields and asymmetries generally lead to a chaotic flow behavior. At moderate amplitudes, we have followed the process of the horizontal layer folding (or horizontal chevron domain formation) and the smectic C* layer reorientation of ferroelectric liquid crystals by applying symmetric and asymmetric wave forms, respectively, and performing time resolved x-ray measurements. The studies unambiguously show the formation of a horizontal (in-plane, i.e., in a plane parallel to the cell substrates) chevron domain structure from a nonoriented sample by application of a symmetric electric field of sufficient amplitude. It is then demonstrated that a transition from the horizontal chevron domain structure to an in-plane uniform smectic layer direction takes place on application of asymmetric electric wave forms. Reversal of the field asymmetry reverses the inclination direction and selects the other layer normal direction as the uniform end state. The in-plane smectic layer reorientation process is followed here as it evolves, and analyzed directly by means of x-ray scattering.     

Molecular models for ferroelectric liquid crystals with conventional and anomalously weak layer contraction

A molecular theory of the ferroelectric smectic C* phase has been developed using the simple model of a chiral molecule composed of a uniaxial core and a pair of off-center nonparallel dipoles which determine molecular chirality and polarity. The interaction between uniaxial cores is modeled by a rather general effective potential which can be used to describe smectic materials with both conventional and anomalously weak layer contraction in the smectic C* phase. Spontaneous polarization, tilt, and layer spacing are calculated numerically as functions of temperature, and it is shown that the variation of the polarization generally deviates from that of the tilt angle. It is shown that this deviation is more pronounced in smectic materials tilting with low layer contraction which corresponds to existing experimental data. The model has been used to reproduce qualitatively the experimental data for polarization, tilt and layer spacing for two similar mixtures exhibiting conventional and anomalously weak layer contraction. The polarization and the tilt are also calculated in the case when the smectic A-smectic C* transition is characterized by the biaxial primary order parameter.     

Molecular-statistical approach to a behavior of ferroelectric,antiferroelectric and ferrielectric smectic phases in the electric field

The fundamental theoretical approach derived in A.V. Emelyanenko et al., Phys. Rev. E 74, 011705 (2006) is complemented by a consideration of the influence of the homogeneous electric field on Sm- C _A ^* , biaxial intermediate phases, and Sm-C ^* . The crucial role of the induced polarization is investigated for the first time. The evolution of any tilted smectic phase in the electric field is found to meet the two thresholds. The first threshold corresponds to the unwinding process, and the second one corresponds to the phase transition into the bi-domain structure of Sm-C ^* , where the tilt plane has some contribution either along or against the electric field, while the average direction may still be perpendicular to the electric field. The tilt plane in the monodomain (conventional) structure preceding the second threshold is the same in every unwound phase, and is perpendicular to the electric field. No 3D distortion in Sm- C _A ^* is predicted on application of the electric field. The entire electric-field-temperature phase diagrams including the possibility of existence of the maximal number of tilted smectic phases are plotted and compared with the experimental ones. The numerical calculations in the framework of this fundamental study are done with help of AFLC Phase Diagram Plotter software developed by the author and available at his web page.     

Evidence for triclinic symmetry in smectic liquid crystals of bent-shape molecules.

The first experimental evidence for triclinic symmetry of bulk smectic liquid-crystal samples of achiral banana-shaped molecules is presented. This phase corresponds to the so-called Sm-CG phase consisting of biaxial molecules and characterized by two tilt directions with respect to the layer normal: tilt of the molecular plane (clinic) and tilt of the molecular kink direction (leaning). Each smectic layer has a polarization component normal to the smectic layers (C1 symmetry). The observations suggest that the phase tentatively labeled as B7 is identical with the Sm-CG phase.     

Field-induced phase transitions and reversible field-induced inversion of chirality in tilted smectic phases of bent-core mesogens

Three homologous achiral five-ring bent-core mesogens are presented where 4-chlororesorcinol is the central core and the aromatic rings are linked by ester groups. These compounds form smectic phases with a tilted arrangement of the molecules (tilt angle ≈ 45^°). On cooling the isotropic liquid this phase adopts a fan-like texture which shows for two homologues at relatively high electric fields ( 25-35V μm^-1) an antiferroelectric electro-optical response based on the collective rotation of the molecules around their long axes. At lower temperature the application of a sufficiently high electric field leads to a continuous transition into a non-birefringent texture which exhibits randomly distributed domains of opposite handedness. These domains can be reversibly switched into a state of opposite chirality by reversal of the field polarity. This switching is bistable and shows a current response typical for a ferroelectric ground state. The possible mechanism of the field-induced phase transition, of the ferroelectric switching and of the field-induced inversion of the chirality is discussed on the base of XRD, ¹³C- and ¹H-NMR investigations, dielectric and electro-optical measurements.     

Piezoelectric effect in liquid crystals

A piezoelectric effect has been observed in a cholesteric liquid crystal layer (an electric field effect type, a mixture of cholesteryl oleyl carbonate, cholesteryl chloride and cholesteryl nonanoate) [1]. The layer, subjected to shear vibration, generates an alternating electric potential of the same frequency as the exciting vibration. In the present paper an extension of these investigations is reported to cases with various mixing ratios and also to one of smectic liquid crystals (lecithin with water). For a cholesteric liquid crystal of a particular mixing ratio, the strength of the electric generation is found to reach as high as 450 mV(p-p) for a vibratory shear displacement of 1 μm(p-p) under a certain molecular orientation preparation. Small electric generation is also observed for the above smectic liquid crystal but not for the nematic liquid crystals (MBBA and EBBA). A simple continuum elasticity model can qualitatively explain the behaviour of this electric potential generation.     

Order and strain in main-chain smectic liquid-crystalline polymers and elastomers

The layer correlations in main-chain smectic liquid-crystal polymer and elastomer systems have been studied using high-resolution X-ray scattering. In contrast to side-chain smectic polymers, in main-chain systems the polymer chains are oriented parallel to the layer normal. As a result they couple directly to the lamellar structure and any polymer defect is translated into layer distortions. For the homopolymers the resulting X-ray lineshapes are well described by Lorentzians. This is interpreted as an average of algebraically decaying order in domains with dimensions of hundreds of nm and a wide dispersion of sizes. The elastomers show much broader peaks than the correponding polymers. This is attributed to strong non-uniform strain within the finite-size domains due to defects of the layer structure. An erratum to this article is available at .     

Critical behaviour of the smectic A*–C* phase transition and electroclinic effect of ferroelectric liquid crystals with terphenyl rigid core

The SmA*–SmC* phase transition was studied by measuring the temperature and electric field dependences of the optical tilt angle, the electric polarisation and the dielectric spectra collected in a wide frequency range. Critical behaviour of the phase transition was analysed by varying the length of the fluorinated part of the alkyl terminal chain and by differing fluorine substitution in the terphenyl core. Both tilt and polarisation show tricritical mean-field behaviour for all homologues with n?>?2. Almost all coefficients that describe the SmA*–SmC* transition in the frame of the Landau theory were derived for homologue series. Double fluorine substitution in the central ring of the core seems to promote the ‘de Vries'-type smectic A*–C* phase transition with a little layer shrinkage. These well correspond with the lower tilt angle and smaller changes of the birefringence at the phase transition compared to the other homologues.     

Effect of chiral solute on the smectic a to C phase transition of second order

The Landau theory is applied to explain the helicoidal effect of a chiral solute on an ordinary smectic C state below a smectic A-C phase transition of second order. It is shown that T_c increases with the concentration c of the solute, for small c. We suggest that a simultaneous application of electric and magnetic fields perpendicular to the smectic layers might, in some cases, also make the C phase helicoidal.     

Helix unwinding in ferroelectric liquid crystals induced by tilted electric field

Helix unwinding in ferroelectric liquid crystals induced by an electric field is theoretically studied on the basis of the continuum theory. By applying a weak electric field tilted to the smectic layers, the contribution of the dielectric interaction energy density to the total free energy density is increased. Approximation methods are used to calculate the free energy for different tilt angles between the electric field and the smectic layers. The obtained results suggest selecting the optimal number of pitches in the film that matches to the minimum of the free energy.     

Ferroelectric smectic phase formed by achiral straight core mesogens

We report electro-optic experiments in liquid crystalline freestanding films of achiral hockey stick shaped mesogens with a straight aromatic core. The material forms two smectic mesophases. In the higher temperature phase, a spontaneous polarization exists in the smectic layer plane and the films show polar switching in electric fields. It is the first example of a ferroelectric phase formed by nearly rodlike achiral mesogens. Mirror symmetry of the phase is spontaneously broken. We propose a molecular configuration similar to a synclinic ferroelectric (C(S)P(F)) high temperature phase and an anticlinic, probably antiferroelectric (C(A)P(A)) low temperature phase.     

Phase transition to anticlinic texture in free-standing smectic c films

Experimental data on the optical reflectance of free-standing smectic C films were analyzed within the framework of a phenomenological Landau approach. At a certain temperature T _0N (determined from experimental data), which exceeds the known temperature T _c of the volume phase transition from smectic A to smectic C state, a surface phase transition takes place whereby molecules in the surface layer become sloped relative to the normal of the smectic layers. The transition temperatures T _0N ^s,a for N-layer films possessing synclinic (symmetric) and anticlinic (antisymmetric) textures of the order parameter (tilt angle θ) were determined. A comparison of the theoretical and experimental data allowed all parameters of the model to be determined (including critical indices of the correlation length and the surface order parameter). Three possible models of the transition from the state with transverse polarization (perpendicular to the molecular tilt plane) to the state with longitudinal polarization (parallel to this plane) are analyzed. The transition takes place at low (°–°) values of the order parameter θ in the middle layer of the film.     

The structure of the smectic phases of terephthal-bis-(butylaniline) studied by electron spin resonance spectroscopy

Electron spin resonance (E.S.R.) measurements at X-band (3·3 kG) of the spin probe 17β-hydroxy-4,4′-dimethylspiro[5α-androstane-3,2′-oxazolidin]-3′-yloxyl dissolved in the smectic phases (A, C and B) of the mesogen 4,4′-terephthal-bis(butylaniline) (TBBA) are reported. Two types of samples were studied in the dependence on temperature, sample orientation and strength of the magnetic field: (i) glass plate sandwiches with less than 0·1 mm of the mesogen, and (ii) 4 mm i.d. cylindrical glass tube. The sandwich samples were prepared as monodomains with the smectic layers parallel to the glass plates. In these samples the orientation of the layers and of the director is fixed and cannot be reoriented even in a magnetic field of 21 kG. From the angular dependence of the spectrum, the tilt angle, the order parameter and their temperature dependence were determined.

In the cylindrical samples the original orientation of the smectic layers is preserved, and up to about 3 kG the director's orientation with respect to the sample is almost unaffected in all smectic phases. On subjecting the sample to higher fields (～ 20 kG) the director in the smectic C phase will re-align so as to minimize the magnetic energy, subject to the fixed tilt angle. The new alignment is preserved when the strength of the magnetic field is reduced. No such re-alignment is observed in the smectic B phase even after subjecting the sample to a field of 21 kG, in contrast to previous deuterium N.M.R. measurements at 14 kG. It is suggested that in this phase the director is pulled by strong fields but relaxes to its original direction when the magnetic field is brought back to 3·3 kG.     

Hunting for smectic C in calamitic azobenzene ionic liquid crystals with different cationic head groups

The tilted smectic C phase is a rather uncommon phase in ionic liquid crystals (ILCs), whereas the orthogonal smectic A phase is the most common phase in ILCs. We now present 2 new groups of mesogens with an azobenzene core that exhibit smectic C as well as smectic A phases. Their phase sequences and tilt angles were studied by polarizing microscopy, and their temperature‐dependent layer spacings and orientational order parameters were investigated by X‐ray diffraction. We present 1 new amidinium azobenzene mesogen that forms enantiotropic smectic C and A phases and another amidinium as well as 2 new guanidinium azobenzene mesogens that exhibit monotropic smectic C and enantiotropic smectic A phases. With this study, we show that azobenzene is indeed an SmC‐promoting group in ILCs. Comparing these results with our earlier results on azobenzenes with an N‐methylimidazolium head group (N Kapernaum et al, ChemPhysChem 2016, 17, 4116‐4123), we show that the aromaticity of the imidazolium head group plays an important role in the formation of smectic C phases.