A nematic to nematic transformation exhibited by a rod-like liquid crystal.

A novel, highly polar rod-like liquid crystal was found to exhibit two distinct nematic mesophases (N and NX). When studied by microscopy and X-ray scattering experiments, and under applied electric fields, the nematic phases are practically identical. However, calorimetry experiments refute the possibility of an intervening smectic mesophase, and the transformation between the nematic phases was associated with a weak thermal event. Analysis of measured dielectric data, along with molecular properties obtained from DFT calculations, applying the Maier-Meier relationship allowed for the degree of antiparallel pairing of dipoles in both nematic phases to be quantified. Based on the results, we conclude that the onset of the lower temperature phase is driven by the formation of antiparallel molecular associations.

Self-organizing behaviour of glycosteroidal bolaphiles: insights into lipidic microsegregation.

In this article we describe work on the synthesis of bolaphile biomimics composed of glucose head groups and steroidal units linked together by a methylene chain of varying length. The condensed phases formed by self-organization of the products as a function of temperature were characterized by differential scanning calorimetry and thermal polarized light microscopy. The results of these studies show that the thermal stabilities of the lamellar mesophases formed vary linearly as a function of increasing aliphatic composition, which reflects a linear hydrophobic-hydrophilic balance with respect to transition temperatures.

Synthesis and characterisation of an unsymmetrical, ether-linked, fluorinated bimesogen exhibiting a new polymorphism containing the N(TB) or 'twist-bend' phase.

In this article we report on the liquid crystal phases and properties of the bimesogen 4-((11-((4'-fluoro-[1,1'-biphenyl]-4-yl)oxy)undecyl)oxy)-2,3-difluoro-4'-(4-propylcyclohexyl)-1,1'-biphenyl. This material was shown to exhibit an Iso Liq-N-NTB-SmA phase sequence, thereby clearly indicating that the NTB phase possesses an ordering of the constituent molecules that is between that of a conventional nematic and the smectic A phase. This compound allows us to better understand the relationship between molecular structure and the NTB phase, and we conclude it is the gross topology that dictates the incidence of this fascinating phase and not molecular properties such as dipole moment and bend angle.

Understanding the distinctive elastic constants in an oxadiazole bent-core nematic liquid crystal.

The splay and bend elastic constants of the bent-core oxadiazole material [C5-Ph-ODBP-Ph-OC12] have been investigated as a function of temperature across the nematic phase. The bend constant K(33) is found to take values of ~3.0 pN and to be almost temperature independent, whereas, the splay constant K(11) increases monotonically from ~3.5 pN close to the isotropic phase transition to values of ~9 pN deep in the nematic phase. No pretransitional divergence is observed in either K(11) or K(33) at temperatures approaching the underlying phase. This behavior of the elastic constants is distinct from that observed in rodlike liquid crystal systems but appears to share characteristics with the few other bent-core nematic systems studied to date. We discuss the interdependence of the elastic constants, the birefringence, and the order parameter to allow a comparison of the observed behavior with theory. We show that calculations of the elastic constants via molecular-field theory and atomistic modeling are in excellent qualitative as well as good quantitative (within 2 pN) agreement with the measurements across the temperature range, offering a deeper understanding of the elasticity in bent-core nematic materials than has been, hitherto, available.

Nonstandard electroconvection in a bent-core oxadiazole material.

Electroconvection (EC) phenomena have been investigated in the nematic phase of a bent-core oxadiazole material with negative dielectric anisotropy and a frequency dependent conductivity anisotropy. The formation of longitudinal roll (LR) patterns is one of the predominant features observed in the complete frequency and voltage range studied. At voltages much above the LR threshold, various complex patterns such as the "crisscrossed" pattern, bimodal varicose, and turbulence are observed. Unusually, the nonstandard EC (ns-EC) instability in this material, is observed in a regime in which we measure the dielectric and conductivity anisotropies to be negative and positive respectively. A further significant observation is that the EC displays distinct features in the high and low temperature regimes of the nematic phase, supporting an earlier report that EC patterns could distinguish between regions that have been reported as uniaxial and biaxial nematic phases.

Evolution of a rare sequence of surface transitions with temperature and film thickness.

In free-standing smectic films, layers near the surfaces of the film often contain molecules tilted away from the layer normal, while in the bulk of the film the magnitude of the tilt decays exponentially with distance from the surface. We have identified the detailed molecular tilt orientations in the surface layers of films for one antiferroelectric liquid crystal compound. A series of five surface structures exists with different nonplanar tilt arrangements for each structure. The molecular orientations in the surface layers evolve with temperature. The polarization of the film also evolves with temperature, corresponding to the tilt arrangements. Using ellipsometric data, we reconstruct the changes in the magnitude and azimuthal direction of the tilt as functions of temperature. We have also studied films of several different thicknesses. We present a phase diagram for the five surface structures showing the dependence on temperature and film thickness.

Propagation of an electromagnetic wave in an absorbing anisotropic medium and infrared transmission of liquid crystals: comparison with experiments.

The theory of the absorbance of a semi-infinite medium characterized by a second-rank dielectric tensor for the entire electromagnetic spectrum, as given by Scaife and Vij [J. Chem. Phys. 122, 174901 (2005)], is extended to include molecules of prolate spheriodal shape with longitudinal and transverse polarizabilities and to cover the case of elliptically polarized incident radiation. The theory is applied to the infrared transmission experiments of biaxial liquid crystals. It is found that the formula for the dependence on frequency and on angle of polarization of the absorbance A(omega,theta)= -log(10)[10(A(omega,0)) cos(2) theta + (10(-A(omega,pi/2)) sin(2) theta)] is unaffected by the anisotropy of the molecules and by the elliptical polarization of the incident radiation. A small (+/-5%) discrepancy between theory and experiment has been found for bands with high absorbances. It is found that this discrepancy does not depend on birefringence of the sample but may depend on the precise method of absorbance measurement and on effects at the surface of the cell containing the liquid crystal under test.

Nonplanar tilts in very thin smectic films of one liquid-crystal compound.

Surface effects cause tilted molecular arrangements in smectic layers near the surface of a free-standing liquid-crystal film in which the bulk of the film is in the smectic- A phase. One recent work has shown that the tilt directions in adjacent surface layers may be nonplanar. In this paper we study films with thicknesses of two to six smectic layers. Surface effects dominate in these very thin films. We show that the molecular tilts are nonplanar even in these very thin films.

Probing the material properties and phase transitions of ferroelectric liquid crystals by determination of the Landau potential.

The full Landau potential of several, widely varying ferroelectric liquid-crystalline materials has been experimentally determined. Tilt angle and polarisation data is analysed across the SmA to SmC transition for varying applied electric-field amplitudes, allowing the determination of all the coefficients of the generalised Landau model of ferroelectric liquid crystals. The materials investigated encompass different materials, including low-polarisation mixtures to high-polarisation single-component materials. The materials also possess a variation in the order of the SmA to SmC phase transition from strongly first order to strongly second order. The effects of both the polarisation and order of phase transition of the system are discussed with respect to the various terms of the generalised Landau model. Further, the mechanisms behind the difference between a first- and second-order phase transition are discussed with respect to the Landau potential and the second Landau coefficient b .

Thermotropic liquid crystalline glycolipids.

Are the liquid crystalline properties of the materials of living systems important in biological structures, functions, diseases and treatments? There is a growing consciousness that the observed lyotropic, and often thermotropic liquid crystallinity, of many biological materials that possess key biological functionality might be more than curious coincidence. Rather, as the survival of living systems depends on the flexibility and reformability of structures, it seems more likely that it is the combination of softness and structure of the liquid-crystalline state that determines the functionality of biological materials. The richest sources of liquid crystals derived from living systems are found in cell membranes, of these glycolipids are a particularly important class of components. In this critical review, we will examine the relationship between chemical structure and the self-assembling and self-organising properties of glycolipids that ultimately lead to mesophase formation.

Possible model of an antiferroelectric twist grain boundary phase.

Using x-ray and optical methods we have probed the structural organization of an antiferroelectric twist grain boundary phase (TGBC(a)) lying between the regular antiferroelectric smectic-C (SmC(a)* and the smectic-Q (SmQ) or isotropic phase. We find that the twist axis is everywhere perpendicular to the local smectic layer normal and that the helical superstructure is incommensurate with the smectic layer structure. The twist grain boundaries consist of a periodic lattice of alternating +1/2 and -1/2 dispirations, i.e., unit screw dislocations in combination with half unit disclinations. The molecular tilt plane is alternatingly parallel and perpendicular to the twist axis. We find that the optically measured tilt angle in the SmC(a)* phase is smaller than that measured by x rays, which is the opposite to what is found in the SmC* phase. This means that the core part tilts less than the end chains in the SmC(a)* phase, while it tilts more in the SmC* phase. On entering the TGB phase a clear decrease is measured in the tilt angle. This is explained by the elastic influence from the disclinations, which appear in this phase.

Conformational distribution of a ferroelectric liquid crystal revealed using fingerprint vibrational spectroscopy and the density functional theory.

The authors have investigated the conformational structure of the ferroelectric liquid crystal compound 4-3-methyl-2-chloropentanoyloxy-4"-hexyloxy-biphenyl also known under the abbreviations 3M2CPHOB and C6 using vibrational (IR and Raman) spectroscopy. The measured spectra exhibit two bands corresponding to the C=O stretching vibration that are separated by 20 cm(-1). In contrast, the molecular structure comprises only one such group. They assigned the two bands to different conformers that coexist in a temperature range between 25 and 65 degrees C covering the entire mesophase of this material. This assignment is strongly confirmed by calculated vibrational spectra based on the density functional theory.

Discontinuous change in the smectic layer thickness in ferrielectric liquid crystals.

The temperature dependence of the thickness of thick free-standing films is studied using a high-resolution film thickness measurement technique. A small discontinuity in the temperature dependence of the smectic layer thickness at every phase transition between ferro-, ferri-, and antiferroelectric phases is observed. We show that the major contribution to it arises from a change in the smectic tilt angle.

Molecular orientational properties of a high-tilt chiral smectic liquid crystal determined from its infrared dichroism.

The orientational characterisitics and the temperature dependencies of the molecular apparent tilt angle of a partly fluorinated chiral smectic liquid crystal (/S/)-4-(1-methylheptyloxycarbonyl)phenyl 4'-[6-(3,4,4,4-tetrafluoro-3-trifluoromethylbutylcarbonyloxy)hexyloxy] biphenyl-4-carboxylate (acronym MHPHFHHOBC) are studied using the polarized Fourier transform infrared (FTIR) spectroscopy. The molecular orientational distributions and the orientational order parameters for a homogeneously aligned liquid crystalline sample at various temperatures and external electric fields are examined. The analysis uses the dichroic parameters of the phenyl and the carbonyl bands. For a temperature range of 65-80 degrees C corresponding to the antiferroelectric SmCA* phase, the molecular apparent tilt angle lies within the range 43 degrees -44 degrees; antiferroelectric smectic structure being rather close to the orthoconic SmCA* phase. An application of sufficiently high dc field across the cell in its SmA* phase surprisingly shows that the dichroism first increases slowly and then rapidly in two stages and finally a saturated apparent tilt angle of approximately 30 degrees is reached. The IR dichroic data is used to estimate the polar angles and the degree of rotational biasing of the carbonyl groups with respect to the molecular long axis. In the SmA* phase, the sample appears to demonstrate some of the typical properties of a de Vries material.

Investigations of nanoscale helical pitch in smectic-C*alpha and smectic-C* phases of a chiral smectic liquid crystal using differential optical reflectivity measurements.

Differential optical reflectivity (DOR) was used to study the temperature dependence of the short helical pitch in freestanding films of a liquid crystal compound. The experimentally measured DOR signal was fitted using Berreman's 4 x 4 matrix method to get the pitch value in the smectic-C*alpha (sMC*alpha) phase. The results show continuous evolution of the pitch between the smectic-C*alpha and sMC*alpha phases. In sMC*alpha, the pitch decreases as temperature increases and is found to level off at 16+/-1 smectic layers at the sMC*alpha to smectic-A* transition.

Surface-induced multiple reentrant transitions.

We have studied tilted surface layers in the bulk SmA temperature window of one liquid crystal using null transmission ellipsometry. Five distinct nonplanar surface structures were observed. We present analyses of the tilt and azimuthal profiles of the structures and examine the transitions between the structures. The transitions are identified as a double reentrant synclinic-anticlinic-synclinic-anticlinic transition. Meanwhile, the transitions also display reentrant ferroelectric-antiferroelectric-ferroelectric behavior.

Extension of the resonant scattering technique to liquid crystals without resonant element.

We report X-ray resonant scattering experiments performed on the prototype liquid-crystalline compound MHPOBC doped with a chemical probe containing a resonant atom (selenium). We determined directly for the first time the microscopic 3- and 4-layer structure of the ferrielectric subphases (SmC(FI1)* and SmC(FI2)*) present in MHPOBC. Despite the low fraction of the selenium probe, the resonant signal is strong enough to allow an unambiguous determination of the basic structure of the ferrielectric subphases. These experiments demonstrate that the resonant scattering technique can be extended to liquid crystalline materials without resonant element and may stimulate new studies. A non-resonant Bragg reflection was also found in the SmC(FI1)* phase in pure MHPOBC, consistent with the 3-layer distorted model, but never detected before.

Self-assembly of biaxial ordering and molecular tilt angle of chiral smectic liquid crystals in homeotropically aligned cells investigated using infrared spectroscopy.

Temperature dependences of the infrared absorbance have been measured for the four chiral liquid crystal samples in the homeotropic cell configuration. It is shown that the values of the orientational order parameter obtained using this method exhibit a remarkable similarity to the x-ray diffraction results of the smectic layer spacing and lead to accurate values of the molecular tilt angle. This has important consequences for the existing interpretation of the x-ray data. The proposed method, in many cases, may be considered as a valuable alternative to the x-ray diffraction, giving additional, important information about the orientations and the ordering of the molecular fragments. It is found that if the experimentally obtained order parameter is low, then the molecular biaxiality is exceptionally large. The average phenyl ring plane is found to lie close to the molecular tilt plane.

Self-assembled uniaxial and biaxial multilayer structures in chiral smectic liquid crystals frustrated between ferro- and antiferroelectricity.

With a view to obtain a molecular model for the subphases produced by the frustration between ferro- and antiferroelectricity in chiral smectic liquid crystals, we report results on two compounds and observe (i) the staircase character of uniaxial Sm C(*)(alpha) itself in the bulk and (ii) the multipeaked characteristic reflection bands due to the modulated helical structures just above the Sm C(*)(A) temperature range. We suggest the emergence of several uniaxial and biaxial subphases. The results show that both types of subphases can be specified by q(T) = [F] / ( [A] + [F] ) in the zero-order approximation; [A] and [F] are the numbers of antiferroelectric and ferroelectric orderings in the unit cell. We consider the basis of both types of subphases, particularly the description of the short-pitch helical structure of Sm C(*)(alpha), in terms of the molecular models so far proposed and emphasize the important role played by the discrete flexoelectric polarization.