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.     

Direct measurement of tilt angle in smectic mesophases by neutron diffraction

We report the results of a direct measurement of the tilt angle of the molecules with respect to the normal layer in the different smectic phases and in the crystalline phase of the TBBA liquid crystal. The values of the tilt angles are obtained by using a new simple method that consists of direct reading of the angular distance between two Bragg peaks in a single neutron rocking curve. The results on the smectic phases are in good agreement with the existing experimental values obtained with other techniques.     

Direct observation of diffuse cone behavior in de Vries smectic-A and -C phases of organosiloxane mesogens

Simultaneous and direct x-ray measurements of the smectic layer spacing, molecular tilt, and orientational order in the de Vries smectic A (SmA) and C (SmC) phases of two organosiloxane mesogens reveal that (i) the SmC (tilt) order parameter exponent β=0.26±0.01 for 2nd order SmA-SmC transition--in excellent agreement with the tricritical behavior, (ii) the siloxane and hydrocarbon parts of the molecules are segregated and oriented parallel to the director with very different degree of orientational order, and (iii) thermal evolution of the effective molecular length is different in the two phases.     

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.     

Chain dynamics in a chiral C phase by deuteron spin relaxation study

Molecular reorientations and internal conformational transitions of an aligned chiral liquid crystal (LC) 10B1M7 are studied by means of deuterium spin-lattice relaxation in its smectic A (SmA) and smectic C* (SmC*) phase. The motional model which is applicable to uniaxial phases of many LCs is found to be adequate even when the phase is a tilted SmC* phase. The deuterium NMR spectrum in this phase cannot discern rotations of the molecular director about the pitch axis. The basic assumption is that the phase biaxiality is practically unobservable. However, the relaxation rates can be accounted for by the tilt angle between the molecular director and the layer normal in the SmC* phase. The tumbling motion appears to show a higher activation energy upon entering from the uniaxial SmA into the SmC* phase.     

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     

A molecular theory of smectic C liquid crystals made of rod-like molecules

Organic compounds exhibiting the smectic C phase are made of rod-like molecules that have dipolar groups with lateral components. We argue that the off-axis character of the lateral dipolar groups can account for tilt in layered smectics (SmC, SmC*, SmI etc.). We develop a mean-field theory of the smectic C phase based on a single-particle potential of the form U _C ∝ sin(2θ)cosφ, consistent with the biaxial nature of the phase, where θ and φ are the polar and azimuthal angles, respectively. The hard-rod interactions that favour the smectic A phase with zero tilt angle are also included. The theoretical phase diagrams compare favourably with experimental trends. Our theory also leads to the following results: i) a first-order smectic C to smectic A transition above some value of the McMillan parameter α, leading to a tricritical point on the smectic C to smectic A transition line and ii) a first-order smectic C to smectic C transition over a very small range of values of the model parameters. We have also extended the theory to include the next higher-order term in the tilting potential and to include the effect of different tilt angles for the molecular core and the chain in the SmC phase. Received 3 August 2002 RID="a" ID="a"Present address: Department of Physics, Vijaya College, R. V. Road, Bangalore - 560 004, India. RID="b" ID="b"e-mail: nvmadhu@rri.res.in     

Optical activity produced by layer chirality in bent-core liquid crystals

Large optical activity has recently been observed in chiral smectic liquid crystalline phases formed from achiral bent-core molecules. The origin of the optical activity remains unclear and has been attributed to both a helical superstructure and the layer chirality produced by simultaneous tilt and polar ordering of bent-core mesogens in the B2 phase. Here, we directly demonstrate that layer chirality produces optical activity in the well ordered SmC(A)P(A) subphase.     

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.     

Statistical Physics Approach to Liquid Crystals: Dynamics of Mobile Potts Model Leading to Smectic Phase,Phase Transition by Wang–Landau Method

We study the nature of the smectic–isotropic phase transition using a mobile 6-state Potts model. Each Potts state represents a molecular orientation. We show that with the choice of an appropriate microscopic Hamiltonian describing the interaction between individual molecules modeled by a mobile 6-state Potts spins, we observe the smectic phase dynamically formed when we cool the molecules from the isotropic phase to low temperatures (T). In order to elucidate the order of the transition and the low-T properties, we use the high-performance Wang–Landau flat energy-histogram technique. We show that the smectic phase goes to the liquid (isotropic) phase by melting/evaporating layer by layer starting from the film surface with increasing T. At a higher T, the whole remaining layers become orientationally disordered. The melting of each layer is characterized by a peak of the specific heat. Such a succession of partial transitions cannot be seen by the Metropolis algorithm. The successive layer meltings/evaporations at low T are found to have a first-order character by examining the energy histogram. These results are in agreement with experiments performed on some smectic liquid crystals.     

Effect of the chiral chain length on structural and phase properties of ferroelectric liquid crystals

Studies of structural and phase properties obtained on several ferroelectric liquid crystalline materials with 2-alkoxypropionate group used as a chiral centre and without any lateral substitution are presented. In dependence on the chiral chain length these compounds exhibit the cholesteric N* phase, the ferroelectric smectic C* and a low-temperature SmX phase. Values of the spontaneous polarization and spontaneous tilt angle have been determined within the whole range of the SmC* phase. A low-temperature SmX phase has been identified as the orthogonal hexatic SmB* phase. The molecular parameters, namely the layer spacing in the SmC* and SmB* phases and the average intermolecular distances (D) between neighbouring parallel molecules in all investigated phases have been determined using the results of the X-ray diffraction obtained on non-oriented samples. The effect of the chiral chain length on mesomorphic, structural and physical properties of the studied ferroelectric liquid crystalline materials is discussed.     

The cone phase of liquid crystals: Triangular lattice of double-tilt cylinders

We predict the existence of a new defect-lattice phase near the nematic-smectic-C(NC) transition. This tilt-analogue of the blue phase is a lattice of double-tilt cylinders which are disclination lines in the smectic layer normal as well as the c-field. We discuss the structure and stability of the cone phase. We suggest that many ‘nematics’ exhibiting short range layering and tilt order may in fact be in the molten cone phase, which is a line liquid.     

Field-temperature phase diagrams in chiral tilted smectics,evidencing ferroelectric and ferrielectric phases

Usual ferroelectric compounds undergo a paraelectric-to-ferroelectric phase transition when the susceptibility of the electric polarization density changes its sign. The temperature is the only thermodynamic field that governs the phase transition. Chiral tilted smectics may also present an improper ferroelectricity when there is a tilt angle between the average long axis direction and the layer normal. The tilt angle is the order parameter of the phase transition which is governed by the temperature. Although the electric susceptibility remains positive, a polarization proportional to the tilt appears due to their linear coupling allowed by the chiral symmetry. Further complications come in when the chirality increases, as new phases are encountered with the same tilt inside the layers but a distribution of the azimuthal direction which is periodic with a unit cell of two (SmC(A)*, three (SmC(Fi1)*, four (SmC(Fi2)* or more (SmC(alpha)* layers. In most of these phases, the layer normal is a symmetry axis so there is no macroscopic polarization except for the SmC(Fi1)* in which the average long axis is tilted so the phase is ferrielectric. By studying a particular compound with only a SmC(Fi2)* and a SmC(alpha)* phase, we show that we recover the uniformly tilted ferroelectric SmC* when applying an electric field. We are thus led to build field-temperature phase diagrams for this class of compounds by combining different experimental techniques described here.     

Electroclinic effect in free-standing smectic elastomer films

The coupling of the mesogenic tilt in smectic liquid crystals to external electric fields in the layer plane (electroclinic effect) provides an opportunity to control the smectic layer thickness with electric fields. In ordered ferroelectric smectic elastomers it is possible to achieve a macroscopic electromechanical response. The effect is particularly pronounced near the smectic A-to-smectic C^* phase-transition temperature. In this work, the electrostriction of weakly cross-linked smectic elastomers is studied by means of optical interferometry of thin films. Its observed magnitude corresponds to an induced tilt of approximately 7.7°, yielding a layer contraction of 1%, in a 3 MV/m electric field. This value is in agreement with earlier measurements of tilt susceptibility in a structurally similar polymer, but is considerably smaller than previously reported data on elastomers with a comparable chemical structure. PACS 61.30.Vx; 83.80.Va; 77.65.Bn     

Dielectric and electrooptical properties of hockey-stick-shaped liquid crystal with a negative dielectric anisotropy

We investigated dielectric properties of a hockey-stick-shaped liquid crystal (HLC). Two dielectric relaxation modes were observed at 0.91 kHz and 4.51 MHz. The low frequency relaxation modes in isotropic, smectic, and nematic phases are related to the motion of ions, collective tilt fluctuation, and rotation around the long molecular axis, respectively. Meanwhile, the high frequency relaxation modes in nematic and smectic phases was due to the rotation around the short axis of the molecules and hindered by the resistance of the ITO layers. We also examined the electrooptical response of the 5.0 wt% HLC-doped commercial nematic liquid crystal (LC) mixtures. The birefringence of the LC mixture was slightly increased, while the falling time and the rotational viscosity was decreased in the nematic phase.     

Electroclinic liquid crystals with large induced tilt angle and small layer contraction

Optical and x-ray scattering studies of a chiral, organosiloxane smectic-A liquid crystal indicate a large field induced optical tilt of up to 31 degrees accompanied by a very small contraction of the smectic layers. This result suggests that the molecules have a nonzero tilt even with no applied field, and that the primary effect of the field is to induce long range order in the direction of the molecular tilt.     

Freedericksz transition in an anticlinic liquid crystal

It is shown experimentally that a very-long-pitch, surface-stabilized, anticlinic liquid crystal undergoes a two-step electric-field-induced transition to the synclinic phase. The liquid crystal remains undistorted below a threshold field E(th). For E>E(th), a Freedericksz transition occurs, wherein molecules in adjacent smectic layers undergo unequal azimuthal rotations about the layer normal. At higher fields a transition to the synclinic phase occurs via solitary waves.     

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.     

Evidence of the hexagonal columnar liquid-crystal phase of hard colloidal platelets by high-resolution SAXS

A vast majority of compounds with bent core or banana shaped molecules exhibit the phase sequence B₆-B₁-B₂ as the chain length is increased in a homologous series. The B₆ phase has an intercalated fluid lamellar structure with a layer spacing of half the molecular length. The B₁ phase has a two dimensionally periodic rectangular columnar structure. The B₂ phase has a monolayer fluid lamellar structure with molecules tilted with respect to the layer normal. Neglecting the tilt order of the molecules in the B₂ phase, we have developed a frustrated packing model to describe this phase sequence qualitatively. The model has some analogy with that of the frustrated smectics exhibited by highly polar rod like molecules.