Theory of nematic–smectic phase separation in thin twisted liquid crystal cells

Recently it has been shown experimentally by the authors that a highly twisted thin nematic cell at low temperatures can separate into a smectic A region in the middle of the cell surrounded by twisted nematic layers at the boundaries. In this case the twist is expelled into the nematic layers and the nematic–smectic A transition temperature is strongly depressed. We present a thermodynamic theory of such a phase transition in a twisted nematic cell, taking into account that the smectic A slab inside the nematic cell can be stable only if the decrease of free energy in the smectic region overcomes the increase in distortion energy of the twist deformation in the nematic layers plus the energy of the nematic–smectic A interface. In such a system the equilibrium thickness of the smectic A slab corresponds to the minimum of the total free energy of the whole cell, which includes all the bulk and surface contributions. Existing experimental data are at least qualitatively explained by the results of the present theory. This opens a unique possibility to study the properties of the nematic–smectic interface which is perpendicular to the smectic layers.     

Effect of the temperature range of the nematic phase on the induction of a twist grain boundary phase in non-chiral liquid crystals

Recent experimental results suggest that the twist grain boundary phase may be induced in non-chiral smectic liquid crystals by confining the material in a twist cell in which the nematic directors at the two surfaces are perpendicular to each other. However, the effect of the temperature range of the nematic phase on the induction of the twist grain boundary (TGB) phase has not been studied to date. We have performed experiments on non-chiral liquid crystals having the nematic-smectic A (N-SmA) phase transition sequence and confined in a twist cell. It is observed that materials with a second order N-SmA phase transition show characteristics of a TGB phase, but a material with a first order N-SmA transition does not.     

Effect of the temperature range of the nematic phase on the induction of a twist grain boundary phase in non-chiral liquid crystals

Recent experimental results suggest that the twist grain boundary phase may be induced in non-chiral smectic liquid crystals by confining the material in a twist cell in which the nematic directors at the two surfaces are perpendicular to each other. However, the effect of the temperature range of the nematic phase on the induction of the twist grain boundary (TGB) phase has not been studied to date. We have performed experiments on non-chiral liquid crystals having the nematic-smectic A (N-SmA) phase transition sequence and confined in a twist cell. It is observed that materials with a second order N-SmA phase transition show characteristics of a TGB phase, but a material with a first order N-SmA transition does not.     

Study of the nematic electroclinic effect in mixtures

The temperature dependence of the nematic electroclinic effect has been studied in binary mixtures prepared from two chiral compounds with nematic-smectic A-smectic C and nematic-smectic C phase sequences. The data obtained show a substantial difference in the magnitude of the effect, not only with the type of phase sequence, but also with the temperature range of the subsequent smectic A phase. These results suggest that short-range smectic fluctuations can play an important role in the nematic electroclinic effect at least when a smectic C phase is close to the nematic. In addition, the dynamic behaviour of the electroclinic effect has been investigated in the compound with the nematic-smectic A transition. As in previous work, an anomaly in the electroclinic response time has been found around the nematic-smectic A transition. This fact is analysed qualitatively assuming two different mechanisms contributing to the electroclinic effect.     

Tricritical point induced by smectic ordering of a nematic gel

The authors study volume phase transitions of a nematic gel immersed in a liquid crystal (LC) solvent, which shows a second-order nematic-smectic A phase transition (NST). Combining Flory's elastic energy [Principles of Polymer Chemistry (Cornell University Press, Ithaca, 1953)] for a swelling of the gel with the McMillan model [Phys. Rev. A 4, 1238 (1971)] for smectic ordering, the authors calculate the equilibrium swelling of the gel and smectic order parameters as a function of temperature. The authors take into account an attractive interaction parameter c between the gel and LC solvents. On increasing the value of the coupling constant c, a second-order NST of the gel is changed to a first-order one and a continuous volume phase transition of the gel is changed to a discontinuous one. The authors find a tricritical point of the gel induced by smectic ordering.     

Induced smectic phases in phase diagrams of binary nematic liquid crystal mixtures

To elucidate induced smectic A and smectic B phases in binary nematic liquid crystal mixtures, a generalized thermodynamic model has been developed in the framework of a combined Flory-Huggins free energy for isotropic mixing, Maier-Saupe free energy for orientational ordering, McMillan free energy for smectic ordering, Chandrasekhar-Clark free energy for hexagonal ordering, and phase field free energy for crystal solidification. Although nematic constituents have no smectic phase, the complexation between these constituent liquid crystal molecules in their mixture resulted in a more stable ordered phase such as smectic A or B phases. Various phase transitions of crystal-smectic, smectic-nematic, and nematic-isotropic phases have been determined by minimizing the above combined free energies with respect to each order parameter of these mesophases. By changing the strengths of anisotropic interaction and hexagonal interaction parameters, the present model captures the induced smectic A or smectic B phases of the binary nematic mixtures. Of particular importance is the fact that the calculated phase diagrams show remarkable agreement with the experimental phase diagrams of binary nematic liquid crystal mixtures involving induced smectic A or induced smectic B phase.     

A Driven Voltage-Controlled Reversible Electrooptic Effect in a Smectic A Phase II. PVA Anchoring

The driven voltage-controlled reversible electrooptic effect in a smectic A phase with a preceding nematic phase twisted by SiO anchoring, previously discovered (cf. the previous paper) has been studied with polyvinyl alcohol (PVA) anchoring. The unique feature of this novel electrooptic effect in smectic A phases is that it reverses by relaxing when the electric field is removed. For the case of PVA anchoring the reversibility of the effect only occurs near the smectic A-nematic phase transition in the smectic A phase. The temperature region of the reversibility of this effect can be widened with a higher voltage. A comparison with the case of a reversible electrooptic effect in a smectic A with a preceding twisted nematic phase and SiO anchoring is made. The possible application of this electrooptic effect in liquid crystal displays with storage is discussed briefly.     

A Driven Voltage-Controlled Reversible Electrooptic Effect in a Smectic A Phase II. PVA Anchoring

Abstract

The driven voltage-controlled reversible electrooptic effect in a smectic A phase with a preceding nematic phase twisted by SiO anchoring, previously discovered (cf. the previous paper) has been studied with polyvinyl alcohol (PVA) anchoring. The unique feature of this novel electrooptic effect in smectic A phases is that it reverses by relaxing when the electric field is removed. For the case of PVA anchoring the reversibility of the effect only occurs near the smectic A-nematic phase transition in the smectic A phase. The temperature region of the reversibility of this effect can be widened with a higher voltage. A comparison with the case of a reversible electrooptic effect in a smectic A with a preceding twisted nematic phase and SiO anchoring is made. The possible application of this electrooptic effect in liquid crystal displays with storage is discussed briefly.     

A bent-core dopant-induced smectic A* twist state

The phase behaviour of a commercial calamitic ferroelectric liquid crystal mixture, doped with different mesogenic and non-mesogenic bent-core molecules was investigated through polarising microscopy, optical measurements and quenched growth. A twisted smectic structure, similar but not equivalent to a twist grain boundary (TGB) phase, and absent in the neat FLC mixture, was verified. The twisted smectic state can only be observed on cooling and its stability depends on the rate of temperature decrease, which indicates a kinetically governed behaviour. Further, the growth dynamics of the low temperature uniform SmA* bookshelf structure is dominated by viscosity instead of free energy density, as would be expected for a true thermodynamic phase transition. The investigations signify the chiral induction capability of achiral, bent-core dopant molecules and we believe that the observed behaviour represents the onset of TGB formation at very large pitch. It can thus give valuable information for the fundamental physical understanding of twist grain boundary phase formation.     

A bent‐core dopant‐induced smectic A* twist state†

The phase behaviour of a commercial calamitic ferroelectric liquid crystal mixture, doped with different mesogenic and non‐mesogenic bent‐core molecules was investigated through polarising microscopy, optical measurements and quenched growth. A twisted smectic structure, similar but not equivalent to a twist grain boundary (TGB) phase, and absent in the neat FLC mixture, was verified. The twisted smectic state can only be observed on cooling and its stability depends on the rate of temperature decrease, which indicates a kinetically governed behaviour. Further, the growth dynamics of the low temperature uniform SmA* bookshelf structure is dominated by viscosity instead of free energy density, as would be expected for a true thermodynamic phase transition. The investigations signify the chiral induction capability of achiral, bent‐core dopant molecules and we believe that the observed behaviour represents the onset of TGB formation at very large pitch. It can thus give valuable information for the fundamental physical understanding of twist grain boundary phase formation.     

From monomolecular films to bulk liquid crystals

Molecules forming thermotropic liquid crystal bulk phases, were investigated at the air-water interface. With nematic and smectic substances, compression of the film resulted in an increase of the lateral pressure, provided the molecules had an amphiphilic character. Two types of π-A-diagrams were found for areas below a threshold value: (i) A single coexistence region (constant pressure at different areas) is obtained for molecules forming nematic liquid crystal bulk phases. The original monomolecular film grew in the third dimension to form a nematic liquid crystal at the interface. (ii) The π-A-diagram showed several coexistence regions with constant pressures if the molecules had the capacity to form smectic bulk phases. The “collapses” were at areas in the relation 1 : 1/2 : 1/3 etc. suggesting that smectic layers have been formed. The aqueous subphase is found to make a large contribution to the latent heat. The initial layer (together with the subphase) is found to be of lower symmetry than the upper layer(s). The transition is first order at low temperature (< 30°C) and second order at high temperatures. Evidences are given for a smectic Shubnikov phase where the layer-to-layer material flow is concentrated in flux lines.     

Landau-de Gennes theory of the core structure of a screw dislocation in smectic A liquid crystals

We present details of calculations of the core structure of a screw dislocation in a smectic A liquid crystal, using the phenomenological Landau-de Gennes free energy functional. The order parameter frustration created by topological constraints far from the dislocation core is resolved in one of three qualitatively different ways. The three types of dislocation core solution are the DT (double twist), CL (classical), and BP (broken polar symmetry) solutions, respectively. The stability requirements for these structures are discussed, as a function of temperature, smectic elastic properties, and coupling between smectic and nematic order. The effect of possible inhomogeneity between left- and right-handed conformers is also examined.     

Surface ordering at the air–nematic interface. Part 2. A spectroscopic ellipsometry study of orientational order

Spectroscopic ellipsometry has been used to measure enhanced orientational ordering at the nematic–air interface of 8CB as the smectic A phase was approached by cooling from the isotropic phase. The depth profile of the orientational order has been estimated by calculating the ellipsometric parameters for a homeotropic uniaxial surface film on a uniaxial sub‐phase using the Abelès matrix method. This showed that the depth of the enhanced orientationally ordered region was ～10 nm at 0.5°C above the nematic–smectic A transition. This is substantially less than the thickness of the region with surface enhanced smectic order as determined by neutron reflection and a model of the surface structure consistent with both sets of results is proposed.     

NMR determination of smectic ordering of probe molecules

The NMR spectra of the three solutes ortho-, meta-, and para-dichlorobenzene in the nematic and smectic A phases of the liquid crystals 8CB and 8OCB are analyzed to yield two orientational order parameters for each solute. Extrapolation of the asymmetry in the energy parameters that describe the orientational ordering in the nematic phase are used to provide estimates of the strength of the nematic potential in the smectic A phase. The experimentally determined asymmetry of the orientational order parameters in the smectic A phase is then used in conjunction with Kobayashi-McMillan theory applied to solutes to give information about the smectic A layering and the nematic/smectic A coupling. In both smectic A solvents, the solute smectic coupling constant, tau, is negative (with the origin fixed at the center of the smectic layer) for all solutes. The signs and relative values of tau indicate that the ortho and para solutes favor the interlayer region while the meta solute is more evenly distributed throughout the layers.     

Dissipative Particle Dynamics Simulation of the Sensitive Anchoring Behavior of Smectic Liquid Crystals at Aqueous Phase

Rational design of thermotropic liquid crystal (LC)-based sensors utilizing different mesophases holds great promise to open up novel detection modalities for various chemical and biological applications. In this context, we present a dissipative particle dynamics study to explore the unique anchoring behavior of nematic and smectic LCs at amphiphile-laden aqueous-LC interface. By increasing the surface coverage of amphiphiles, two distinct anchoring sequences, a continuous planar-tilted-homeotropic transition and a discontinuous planar-to-homeotropic transition, can be observed for the nematic and smectic LCs, respectively. More importantly, the latter occurs at a much lower surface coverage of amphiphiles, demonstrating an outstanding sensitivity for the smectic-based sensors. The dynamics of reorientation further reveals that the formation of homeotropic smectic anchoring is mainly governed by the synchronous growth of smectic layers through the LCs, which is significantly different from the mechanism of interface-to-bulk ordering propagation in nematic anchoring. Furthermore, the smectic LCs have also been proven to possess a potential selectivity in response to a subtle change in the chain rigidity of amphiphiles. These simulation findings are promising and would be valuable for the development of novel smectic-based sensors.     

Smectic order induced at homeotropically aligned nematic surfaces: a neutron reflection study

Neutron reflection was used to measure the buildup of layers at a solid surface as the smectic phase is approached from higher temperatures in a nematic liquid crystal. The liquid crystal was 4-octyl-4'-cyanobiphenyl (8CB), and the solid was silicon with one of five different surface treatments that induce homeotropic alignment: (i) silicon oxide; (ii) a cetyltrimethylammonium bromide coating; (iii) an octadecyltrichlorosilane monolayer; (iv) an n-n-dimethyl-n-octadecyl-3- aminopropyltrimethyloxysilyl chloride monolayer; and (v) a lecithin coating. The development of surface smectic layers in the nematic phase of 8CB was followed by measuring specular reflectivity and monitoring the pseudo-Bragg peak from the layers. The scattering data were processed to remove the scattering from short-ranged smecticlike fluctuations in the bulk nematic phase from the specular reflection. The pseudo-Bragg peak at scattering vector Q approximately 0.2 A(-1) therefore corresponded to the formation of long-range smectic layers at the surface. The amplitude of the smectic density wave decayed with increasing distance from the surface, and the characteristic thickness of this smectic region diverged as the transition temperature was approached. It was found that the characteristic thickness for some of the surface treatments was greater than the correlation length in the bulk nematic. The different surfaces gave different values of the smectic order parameter at the surface. This suggests that the interaction with the surface is significantly different from a "hard wall" which would give the same values of the smectic order parameter and penetration depths similar to the bulk correlation length. Comparison of the different surfaces also suggested that the strength and range of the surface smectic ordering may be varied independently.     

The Twist Elastic Constant and Anchoring Energy of the Nematic Liquid Crystal 4-N-Octyl-4-Cyanobiphenyl

The twist elastic constant of the nematic liquid crystal 4-n-octyl-4'-cyano-biphenyl (8CB) and the azimuthal anchoring energy at the SiO-nematic interface have been measured by using the torsion pendulum technique. The twist elastic constant of 8CB is found to be systematically larger than that measured by the Freedericksz transition technique. The azimuthal anchoring energy is found to decrease rapidly as the nematic-isotropic transition temperature is approached. This behaviour is analogous to that already reported by us for the nematogen 5CB and can be interpreted by extending the Berreman model of the anchoring energy at a grooved interface.     

Phase Transition and Structural Investigations in 50.5, 50.6 and 50.7

We report X-ray diffraction, density, ultrasonic velocity and refractive index studies in the N(p-n-pentyloxy benzylidene) p-n-alkylaniline compounds, viz. 50.5, 50.6 and 50.7. The nematic-smectic A (NA) transition is found to be weak first order in 50.6 while it is second order in 50.5 and 50.7. The salient features observed are cybotactic clusters in the nematic phase in all the compounds, molecular tilt which was inferred due to the end alkyl chains tilt causing orienta-tional disorder (smaller orientational order parameters 's' than expected) in smectic A phase, smectic F phase and large tilt angle variation in smectic C phase in a small temperature range in 50.5. The observed results are discussed in the light of available data in other n0.m compounds.     

The alignment of a liquid crystal in the smectic A phase in a high surface tilt cell

Liquid crystal alignment is studied using propagating optical mode techniques for a cell with a high surface tilt SiO alignment. The director configuration is determined for both the nematic and smectic A phases. In the nematic phase a uniform splay across the cell is demonstrated, as predicted by continuum theory. In the smectic A phase the structure is seen to be nearly uniform in the central region of the cell with large splay in boundary layers of about 0.5 μm thickness. The reason for this appears to be competition between the tilted surface alignment forces and internal forces within the bulk of the smectic A layer which would induce a homogeneous configuration.