X-ray study of the nematic and smectic A phases of the cyano-substituted pyridines

We report an X-ray study of lamellar ordering in the nematic and smectic A phases of a homologous series of polar liquid crystals, the 2-(4-alkylphenyl)-5-cyanopyridines (nCP). Experiments were carried out using a diffractometer with a linear position sensitive detector. In the nematic and smectic A phases of the nCP and their mixtures with non-polar 4-n-butyl-4′-methoxyazoxybenzene two types of layering were found. One corresponds to the fluctuations of the smectic density wave with a monolayer wavevector q ₁, and the other is due to the partial bilayer fluctuations with the incommensurate wavevector q ₂ ≠ q ₁/2. The temperature dependences of the X-ray scattering intensity and the longitudinal correlation length for both types of layering in the nematic phase are presented. The critical behaviour in the vicinity of the smectic A-nematic phase transition occurs for a fluctuation mode, either q ₁ or q ₂, depending on the position on the liquid crystal phase diagram. The influence of the molecular structure of cyano-substituted pyridines on the formation of layered structures of different types is also discussed.     

X-ray diffraction study of 'side-on fixed' homopolysiloxanes from nematic to smectic C phases

The X-ray patterns for the nematic phase in a series of side-on fixed polysiloxanes show different kinds of diffuse elements which imply complex short range ordering. A systematic structural study of the evolution of the patterns versus two molecular parameters, namely the spacer length and the length of the terminal aliphatic tails, suggests the possible occurrence of a smectic C phase for certain values of these parameters. Taking into account these tendencies, new synthesis led to a nematic-smectic C polymorphism observed for the first time in side-on fixed polysiloxanes.     

Creation of nematic and reentrant nematic phases in bi- and multi-component smectic mixtures

Abstract

Experimental results referring to the transformation of smectic phases, mainly smectic A, into nematic and reentrant nematic phases are reviewed. A new explanation of some experimental results is proposed. Factors which are responsible for the depression of smectic phases in mixtures of polar mesogens are discussed and the possibility of forming mixtures with a broad temperature range of nematic phase from smectic compounds, which can be useful for liquid crystal displays (LCDs), is shown. A nematic gap observed in some cases between monolayer (S_A1) or monolayer and partially bilayer (S_Ad) smectics results from the differences in the organization of the molecules in the smectic layers. It is concluded that polar phase from smectic A₁ phases can be divided into two groups: (a) the first one is characteristic for compounds with the -NCS, -F, -CI, -I or ?COC _m H_{2m + 1} terminal group. The spacing of the smectic layer slowly expands with the increase in alkyl chain length and the structure of the smectic A₁ phase slowly changes to be more like the smectic A_d phase (d/1 > 1). It is proposed that such a smectic is called an enhanced monolayer smectic (S_A1e (b) the second one is typical for compounds with the -CN terminal group. This kind of smectic A₁ phase is rapidly transformed into the smectic A_d phase with increasing alkyl chain length. These latter monolayer mesogens easily form the reentrant nematic phase when they are mixed with other polar smectic mesogens.     

Dielectric relaxation in coexisting nematic and smectic B phases

Mixtures of a polar solute 4-n-pentyl-4'-cyanobiphenyl in a non-polar nematic solvent exhibit two separated low frequency dielectric relaxations for concentrations of the solute between 2 mol% and 20 mol% over a limited temperature range. This behaviour is attributed to coexisting nematic and smectic B phases, in which the polar solute probe has different relaxation frequencies. The observed dielectric spectra can be accurately fitted to two Debye-like relaxations, and the strengths of the absorptions are proportional to the amounts of the coexisting phases. A microscopic determination of the phase diagram confirms the assignment of the coexisting phases, and it is concluded that there is a preference of the dipolar probe molecule for the smectic B phase, which is induced as a result of solute-solvent interactions.     

Creation of a nematic phase in mixtures of smectic A1 phases

Abstract

Phase diagrams were determined for binary mixtures consisting of two 5-n-alkyl-2-(4'-isothiocyanatophenyl)-1,3-dioxane compounds (n-DBT) or 4'-isothio-cyanatophenyl 4-(trans-4'-n-decylcyclohexyl)benzoate and n-DBT. All compounds investigated have monolayer smectic A phases. A nematic phase in the upper temperature range and a nematic gap between two smectic regions also were observed, with the smectic layer spacing ratio, d/d', of 1.23 and 1.87 respectively. The variation of the enthalpy of transition with mixture composition in relation to changes of layer spacing ratio are also discussed for these systems.     

Order parameters and densities in the smectic C, smectic A and nematic phases of a liquid crystal mixture

Measurements of the orientational and translational order parameters for the nematic, smectic A and smectic C phases of a commercial liquid crystal material are reported. The order parameters have been obtained by analysis of the angular distribution of the intensity of X-rays scattered by a sample aligned by a magnetic field. Results are presented as a function of temperature, and it is found that the apparent orientational order parameter in the smectic C phase decreases with decrease in temperature. This is explained using a model of random tilt. The experimental order parameters are compared with those calculated from a mean field model.     

Creation of a nematic phase in mixtures of smectic A1 phases

Phase diagrams were determined for binary mixtures consisting of two 5-n-alkyl-2-(4'-isothiocyanatophenyl)-1,3-dioxane compounds (n-DBT) or 4'-isothio-cyanatophenyl 4-(trans-4'-n-decylcyclohexyl)benzoate and n-DBT. All compounds investigated have monolayer smectic A phases. A nematic phase in the upper temperature range and a nematic gap between two smectic regions also were observed, with the smectic layer spacing ratio, d/d', of 1.23 and 1.87 respectively. The variation of the enthalpy of transition with mixture composition in relation to changes of layer spacing ratio are also discussed for these systems.     

Thermotropic uniaxial and biaxial nematic and smectic phases in bent-core mesogens

Two azo substituted achiral bent-core mesogens have been synthesized. Optical polarizing microscopy and synchrotron X-ray scattering studies of both compounds reveal the existence of the thermotropic uniaxial and biaxial nematic and three smectic phases at different temperatures in these single component small molecule systems. The transition from the uniaxial to biaxial nematic phase is confirmed to be second order. The transitions from the biaxial nematic to the underlying smectic phase and between the smectic phases have barely discernible heat capacity signatures and thus are also second order.     

X-ray studies of the layer thickness in smectic phases

X-ray investigations of nine smectogenic substances exhibiting the smectic A_d, A₁ and crystalline E phases were performed at various temperatures. X-ray patterns yielded the layer thickness d (A_d, A₁ phases) and orthorhombic unit cell parameters (E phase). The layer thickness of the A_d phase in 4'-n-alkyl-4-cyanobiphenyls (nCBs) has different temperature coefficients for shorter (n = 8-10) and longer (n = 12-14) members, which is explained as resulting from two competing effects: a weakening with temperature of the intermolecular association energy that favours an increase in d, and the increasing number of conformers which reduces the molecular length. A small anisotropy of the thermal expansivity in the smectic phases was found by comparing the linear quantity d(T) with the linearized bulk characteristic of the system, V^-3(T), where V = 1/ρ is the specific volume, ρ is the density. Differences between the slopes of the two quantities are less in the case of the A₁ phase of two nDBTs (5-n-alkyl-2-(4'-isothiocyanatophenyl)-1,3-dioxanes). The present X-ray data and recent results of studies of the low frequency relaxation process in these compounds (under atmospheric as well as elevated pressures) give a consistent picture of molecular reorientations around the short axes in the smectic phases.     

Side-on fixed polysiloxanes and 'diluted' copolysiloxanes with nematic and smectic C phases

The influence of the molecular parameters of side-on fixed liquid crystal polymers (LCP), namely the spacer length, the aliphatic tail length and the proportion of mesogenic groups ('dilution' effect), on the mesomorphic, thermodynamic and structural properties of the nematic and smectic C phases has been studied. This shows in particular the stabilization of the SmC phase on increasing the terminal chain lengths. Moreover, this paper provides evidence for an original behaviour in the SmC organization of side-on LCP with a nonstructural monotonous evolution of the thermodynamic and properties with the 'dilution'. Finally, a comparison with side-end LCP can be established : the question of the participation of the polymer backbone in the smectic organization in side-on LCP is raised.     

X-ray study of the highly ordered smectic phases of N-pentyl-N'-(p-pentyloxyphenyl)piperazine

The structures of the highly ordered liquid crystalline smectic phases of N-pentyl-N'-(p-pentyloxyphenyl)piperazine are identified using X-ray diffraction methods. For this compound a phase sequence hexagonal smectic B (S_B)-orthofrhombic crystalline smectic H (C_H)-monoclinic crystalline smectic H (C_H) is observed for the first time. The changes in structural symmetry at the phase transitions are discussed.     

Stability of nematic and smectic phases in rod-like mesogens with orientation-dependent attractive interactions

The stability of isotropic (I), nematic (N), smectic A (Sm A), and hexatic (Hex) liquid crystalline phases is studied for a fluid of molecules with a rod-like shape and dispersive interactions dependent on orientation. The fluid is modeled with the spherocylindrical Gay-Berne-Kihara interaction potential proposed in a recent work, with parameters favoring parallel pair orientations. The liquid crystal phase diagram is characterized for different molecular aspect ratios by means of Monte Carlo simulations in the isobaric-isothermal ensemble. Three types of triple points are observed, namely, I-Sm A-Hex, I-N-Sm A, and N-Sm A-Hex, leading to island-shape domains for the smectic A phase. The resulting phase diagrams are compared with those derived previously for prolate fluids of ellipsoidal and spherocylindrical symmetry. It is concluded that the stability of the layered phases with respect to the nematic phase is enhanced in the spherocylindrical fluids due to geometrical constraints. Furthermore, the anisotropy of the dispersive interactions induces a stronger dependence of the overall phase diagram on temperature and aids in the energetic stabilization of the hexatic crystalline phase with respect to the fluid smectic A phase.     

Model-independent structure and resonant X-ray spectra of intermediate smectic phases

It is shown that the orientational structure of intermediate smectic phases can be determined using the symmetry properties of the general free energy with arbitrary orientational coupling between smectic layers, without addressing a particular model. The structure of three- and four-layer intermediate phases, obtained in this way, corresponds to experimental data. The same method enables one to predict the structure of intermediate phases with periodicity of five and six layers, which have not been observed experimentally so far. The resonant X-ray spectra of the five- and six-layer intermediate phases with predicted structure have also been calculated. These spectra are characterized by a number of features which enable one to distinguish five-layer and six-layer intermediate phases from phases with smaller periods.     

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.     

The relationship between liquid crystal alignment in the nematic and smectic C* phases

The pretilt angle in the nematic phase is related to two different surface dependent factors, while the quality of surface stabilized ferroelectric liquid crystal (SSFLC) devices is dependent on only one of them. We have synthesized two series of polyalkyleneimides and found that the pretilt angles for thick nematic cells are not related to the cone angles in SSFLC cells.     

Discrimination in isotropic, nematic, and smectic phases of chiral calamitic molecules: a computer simulation study

Racemic fluids of chiral calamitic molecules are investigated with molecular dynamics simulations. In particular, the phase behavior as a function of density is examined for eight racemates. The relationship between chiral discrimination and orientational order in the phase is explored. We find that the transition from the isotropic phase to a liquid crystal phase is accompanied by an increase in chiral discrimination, as measured by differences in radial distributions. Among ordered phases, discrimination is largest for smectic phases with a significant preference for heterochiral contact within the layers.     

X-ray diffraction from the uniaxial and biaxial nematic phases of bent-core mesogens

X-ray diffraction patterns for the uniaxial and biaxial nematic phases exhibited by rigid bent-core mesogens were calculated using a simple model for the molecular form factor and a modified Lorentzian structure factor. The X-ray diffraction patterns depend strongly on the extent of the alignment of the molecular axes as well as the orientation of molecular planes. The X-ray diffraction can be unequivocally used to identify the biaxial nematic phase, study the uniaxial-biaxial phase transition, and estimate the order parameters of the nematic phase.     

Computer simulation of diffuse X-ray scattering by an aligned smectic C-like nematic phase

We report a new method for the quantitative analysis of diffuse X-ray scattering by some disordered smectic phases. Computer simulations of diffuse X-ray scattering are compared with actual diffraction patterns of a series of oriented liquid crystalline polymers TDI-C _m C _n . The simulation shows that both Bragg peaks (spots) and equidistant streaks (diffuse scatterings) are diffracted by one smectic C-like structure in which each of the molecular chains is displaced from its mean position by a random distance Δ _z , along the chain axis (z). This is a first type of disorder. By assuming a Gaussian distribution of the disordered displacements, the mean value of Δ _z has been determined from the position and intensity of the streaks and Bragg peaks for the polymers.