Possible new phase of antagonistic nematogens in a disorienting field

A simple model is proposed for nematogenic molecules that favor perpendicular orientations as well as parallel ones. (Charged rods, for example, show this antagonistic tendency.) When a small disorienting field is applied along z, a low-density phase N- of nematic order parameter S(z)<0 coexists with a dense biaxial nematic N(b). (At zero field, N- becomes isotropic and N(b) uniaxial.) But at stronger fields, a new phase N+4, invariant under pi/2 rotations around the field axis, appears in between N- and N(b). Prospects for finding the N+4 phase experimentally are briefly discussed.     

Photopyroelectric investigation of binary mixtures of liquid crystals in contact preparations

The photopyroelectric (PPE) method is proposed as a sensitive technique to study a binary mixture of liquid crystals in a contact preparation. The photothermal signal is generated while scanning the contact preparation. The crystal (K)/smectic-A (S _A), smectic-A/nematic (N), and nematic/isotropic (I) interphase boundaries are detected. The displacement of these boundaries due to the variation of the temperature is monitored. Received: 13 Oktober 1998 / Accepted: 7 July 1999 / Published online: 3 December 1999     

Detecting columnar deformations in a supermesogenic octapode by proton NMR relaxometry

We used proton ( ¹H nuclear magnetic relaxation (NMR) dispersions to study the molecular dynamics in the isotropic phase and mesophases (nematic and columnar hexagonal) of a supermesogenic octapode formed by laterally connecting calamitic mesogens to an inorganic silsesquioxane cube through flexible spacers. The dispersions of the spin-lattice relaxation time (T₁) are interpreted through relaxation mechanisms used for the study of molecular dynamics in low-molar-mass liquid crystals but adapted to the case of liquid crystalline supermolecules. At high frequencies (above 10MHz) the behaviour of the T₁ with the Larmor frequency is similar for all phases and is ascribed to local reorientations and/or rotations. At intermediate and low frequencies (below 10MHz) our results show notable differences in the T₁ behaviour with respect to the mesophases. The nematic (N) and isotropic (Iso) phases’ low-frequency results are similar and are interpreted for both phases in terms of order director fluctuations (ODF), revealing that even in the isotropic phase local nematic order is detected by proton NMR relaxometry. Local nematic order in the Iso phase is interpreted in terms of the presence of nematic cybotactic clusters induced by the interdigitation of mesogens that is promoted by the silsesquioxane octapode molecular structure. In the columnar hexagonal (Col _h phase, the T₁ dispersions show that elastic columnar deformations (ECD) dominate the nuclear magnetic relaxation below 10MHz. This result shows that the columnar packing of the octapode clearly restricts the collective fluctuations of the mesogenic units inspite of their local nematic order.     

Kinetic pathways for the isotropic-nematic phase transition in a system of colloidal hard rods: a simulation study

We study the kinetic pathways for the isotropic-to-nematic transition in a fluid of colloidal hard rods. In order to follow the formation of the nematic phase, we develop a new cluster criterion that distinguishes nematic clusters from the isotropic phase. Applying this criterion in Monte Carlo simulations, we find spinodal decomposition as well as nucleation and growth depending on the supersaturation. We determine the height of the nucleation barrier and we study the shape and structure of the cluster. More specifically, we find ellipsoidal nematic clusters with an aspect ratio of about 1.7 and a homogeneous nematic director field. Our results are consistent with theoretical predictions on the shape and director field of nematic tactoids. Classical nucleation theory gives reasonable predictions for the height of the nucleation barrier and the critical nucleus size.     

Synthesis and mesomorphic behaviors of a series of heterocyclic pyridine-imine-ester based liquid crystals

ABSTRACT

A series of new calamitic liquid crystals, 4-{[(5-methylpyridin-2-yl)imino]methyl}phenyl 4-alkoxybenzoates were synthesized. This series consists of nine members wherein they are differed by the length of alkoxy chain. Spectral analysis results were in accordance with the expected structure. Their thermotropic behaviors were analyzed with Differential Scanning Calorimetry (DSC), Polarizing Optical Microscopy (POM) and powder X-ray diffraction techniques. First member with the shortest alkoxy chain (n?=?2) is a non-mesogen. As the alkoxy chain increased to n?=?4, the monotropic nematic phase appeared. An enantiotropic mesophase (nematic) was observed for the following three members (n?=?6, 8, 10). As the alkoxy chain increased to n?=?12, enantiotropic nematic phase exhibited together with monotropic smectic A (SmA) phase. As the alkoxy chain continuously increased to n?=?14 and 16, enantiotropic phases were observed for both N and SmA. When moving to n?=?18, the nematic phase disappeared and this compound only exhibited a single mesophase (SmA).     

Enhancement of optical nonlinearity in a guest-host system by nematic ordering

Second-harmonic generation (SHG) has been studied for understanding the enhancement mechanism for the second-order optical nonlinearity by the nematic (or axial) ordering in a liquid crystal doped with one-dimensional nonlinear optical (NLO) organic molecules. An extended version of the Maier-Saupe mean-field theory for nematic liquid crystals was developed to obtain analytical expressions for the second-order NLO coefficients in terms of the axial order, the polar order and the effective nematic potential. From the SHG data in a guest-host system composed ofN,N'-dimethylaminonitrostilbene molecules (0.5% by weight) and a liquid crystal, the enhancement of the second-order NLO coefficient,d ₃₃, by nematic ordering becomes almost 3, which agrees well with our theoretical predictions.     

Biaxial nematic phase in model bent-core systems

We determine the bifurcation phase diagrams with isotropic (I), uniaxial (N(U)) and biaxial (N(B)) nematic phases for model bent-core mesogens using Onsager-type theory. The molecules comprise two or three Gay-Berne interacting ellipsoids of uniaxial and biaxial shape and a transverse central dipole. The Landau point is found to turn into an I-N(B) line for the three-center model with a large dipole moment. For the biaxial ellipsoids, a line of Landau points is observed even in the absence of the dipoles.     

Dielectric investigations in the nematic and hexatic smectic B phases of 4-hexyl-4′-[2-(4-isothiocyanatophenyl)ethyl]-1,1′-biphenyl

Temperature-dependent dielectric characterization of 4-hexyl-4′-[2-(4-isothiocyanatophenyl)ethyl]-1,1′-biphenyl (HIEB), which exhibits smectic B and nematic phases, has been carried out over the frequency range of 1 Hz to 10 MHz for homeotropic and planar alignment of sample molecules. This compound shows positive dielectric anisotropy (Δε = ε _∥ ? ε _⊥ > 0) in the nematic (N) phase. One mode of dielectric relaxation showing Arrhenius behaviour has been detected in the hexatic smectic B (SmB) phase. Various electrical parameters, namely, dielectric anisotropy, relaxation frequency and activation energy, have been determined in the N and SmB phases.     

Crystal → nematic phase transition in the liquid crystalline system 1‐isothiocyanato‐4‐(trans‐4‐propylcyclohexyl) benzene (3CHBT) probed by temperature‐dependent micro‐Raman study and DFT calculations

Raman spectra of 3CHBT in unoriented form were recorded at 14 different temperature measurements in the range 25–55 °C, which covers the crystal → nematic (N) phase transition, and the Raman signatures of the phase transition were identified. The wavenumber shifts and linewidth changes of Raman marker bands with varying temperature were determined. The assignments of important vibrational modes of 3CHBT were also made using the experimentally observed Raman and infrared spectra, calculated wavenumbers, and potential energy distribution. The DFT calculations using the B3LYP method employing 6‐31G functional were performed for geometry optimization and vibrational spectra of monomer and dimer of 3CHBT. The analysis of the vibrational bands, especially the variation of their peak position as a function of temperature in two different spectral regions, 1150–1275 cm⁻¹ and 1950–2300 cm⁻¹, is discussed in detail. Both the linewidth and peak position of the ( C H ) in‐plane bending and ν(NCS) modes, which give Raman signatures of the crystal → N phase transition, are discussed in detail. The molecular dynamics of this transition has also been discussed. We propose the co‐existence of two types of dimers, one in parallel and the other in antiparallel arrangement, while going to the nematic phase. The structure of the nematic phase in bulk has also been proposed in terms of these dimers. The red shift of the ν(NCS) band and blue shift of almost all other ring modes show increased intermolecular interaction between the aromatic rings and decreased intermolecular interaction between two  NCS groups in the nematic phase. Copyright © 2009 John Wiley & Sons, Ltd.     

Imperfections in focal conic domains: the role of dislocations

It is usual to think of focal conic domains (FCDs) as perfect geometric constructions in which the layers are folded into Dupin cyclides about an ellipse and a hyperbola that are conjugate. This ideal picture is often far from reality. We have investigated in detail the FCDs in several materials that have a transition from a smectic A (SmA) to a nematic phase (N). The ellipse and the hyperbola are seldom perfect, and the FCD textures also suffer large transformations (in shape and/or in nature) when approaching the transition to the nematic phase, or appear imperfect on cooling from the nematic phase. We interpret these imperfections as due to the interaction of FCDs with dislocations. We analyze theoretically the general principles subtending the interaction mechanisms between FCDs and finite Burgers vector dislocations, namely the formation of kinks on disclinations, to which dislocations are attached, and we present models relating to some experimental results. Whereas the principles of the interactions are very general, their realizations can differ widely in function of the boundary conditions.     

Nematic order-disorder state transition in a liquid crystal analogue formed by oriented and migrating amoeboid cells

In cell culture, liquid crystal analogues are formed by elongated, migrating, and interacting amoeboid cells. An apolar nematic liquid crystal analogue is formed by different cell types like human melanocytes (=pigment cells of the skin), human fibroblasts (=connective tissue cells), human osteoblasts (=bone cells), human adipocytes (=fat cells), etc. The nematic analogue is quite well described by i) a stochastic machine equation responsible for cell orientation and ii) a self-organized extracellular guiding signal, E₂, which is proportional to the orientational order parameter as well as to the cell density. The investigations were mainly made with melanocytes. The transition to an isotropic state analogue can be accomplished either by changing the strength of interaction (e.g. variation of the cell density) or by influencing the cellular machinery by an externally applied signal: i) An isotropic gaseous state analogue is observed at low cell density (melanocytes/mm^2) and a nematic liquid crystal state analogue at higher cell density. ii) The nematic state analogue disappears if the bipolar shaped melanocytes are forced to become a star-like shape (induced by colchicine or staurosporine). The analogy between nematic liquid crystal state analogue formed by elongated, migrating and interacting cells and the nematic liquid crystal phase formed by interacting elongated molecules is discussed. Received 2 August 1999 and Received in final form 5 January 2000     

Fluctuation shift of the nematic–isotropic phase transition temperature

A macroscopic counterpart to the microscopic mechanism of the straightening dimer mesogens conformations, proposed recently by S.M. Saliti, M.G. Tamba, S.N. Sprunt, C. Welch, G.H. Mehl, A. Jakli, and J.T. Gleeson [Phys. Rev. Lett. 116, 217801 (2016)] to explain their experimental observation of the unprecedentedly large shift of the nematic–isotropic transition temperature is discussed. The proposed interpretation is based on singular longitudinal fluctuations of the nematic order parameter. Since these fluctuations are governed by the Goldstone director fluctuations, they exist only in the nematic state. External magnetic field suppresses the singular longitudinal fluctuations of the order parameter (similarly as is the case for the transverse director fluctuations, although with a different scaling over the magnetic field). The reduction of the fluctuations changes the equilibrium value of the magnitude of the order parameter in the nematic state. Therefore, it leads to additional (with respect to the mean field contribution) fluctuation shift of the nematic–isotropic transition temperature. Our mechanism works for any nematic liquid crystals, however the magnitude of the fluctuation shift increases with decrease in the Frank elastic moduli. Since some of these moduli supposed to be anomalously small for so-called bent-core or dimer nematic liquid crystals, just these liquid crystals are promising candidates for the observation of the predicted fluctuation shift of the phase transition temperature.     

Thin nematic films: Anchoring effects and stripe instability revisited

We study theoretically the formation of long-wavelength instability patterns observed at spreading of nematic droplets on liquid substrates. The role of surface-like elastic terms in nematic films of submicron thickness is (re)examined by extending our previous work to hybrid aligned nematics. We identify the upper threshold for the formation of stripes and compare our results with experimental observations. We find that the wavelength and the amplitude of the in-plane director undulations can be related to the small but finite azimuthal anchoring. Within a simplified model we analyse the possibility of non-planar base state below the Barbero–Barberi critical thickness.     

Comprehensive studies on dielectric properties of p-methoxy benzylidene p-decyl aniline with function of temperature and frequency in planar geometry: A potential nematic liquid crystal for display devices

The dielectric properties of the nematic mesophase, p-methoxy benzylidene p-decyl aniline(MBDA), measured in planar geometry with a function of frequency and temperature are investigated in detail. The complex dielectric permittivity(ε' and ε') is also studied at a bias voltage of 10 V for planar aligned sample cell of nematic mesophase. The dielectric permittivity with bias voltage attains a higher( 2 times) value than that without bias voltage at a temperature of 56℃,which is due to the fact that the linking group of nematic molecules is internally interacted with an applied bias voltage.This is supported by observing an enhanced dielectric permittivity of nematic liquid crystal(LC) in the presence of bias voltage, which can be fully explained as the increasing of the corresponding dipole moment. The dielectric relaxation behaviors of nematic LC are also demonstrated for planar aligned sample cell. The remarkable results are observed that the relaxation frequency shifts into low frequency region with the increase of the bias voltage applied to the planar aligned sample cells. The dielectric relaxation spectra are fitted by Cole–Cole nonlinear curve fitting for nematic mesophase in order to determine the dielectric strength.     

Structure,elasticity and phase transitions in liquid crystals with deformations

ABSTRACT

A molecular-statistical theory describing the nematic liquid crystals (LCs) with spherical inclusions (or point defects) is proposed. At given size of inclusions and nematic order parameters at the surfaces of inclusions (zero in the case of point defects) and far from inclusions (where the nematic LC is almost uniform), the distribution of nematic order parameters in the bulk of LC with inclusions was found to be fully determined by the elastic constants of LC. We have found and explained the two-step heat-driven transformation from the nematic phase into the isotropic phase, with the intermediate phase in between. The nematic order parameters and the elastic constants are evaluated in the framework of a unified approach based on the features of pair interaction potentials of the individual LC molecules. It is shown that, in the case of K₃₃ < K₁₁, the point defects should destroy the conventional nematic phase.     

Study of dipole dynamics and pre-transitional effects at isotropic to nematic phase transition by low-frequency dielectric relaxation measurements

Thermal microscopy (TM) as well as low-frequency (LF) dielectric relaxation studies are carried out on a nematic liquid crystal (NLC), viz E7 (Merck Ltd, UK). The isotropic to nematic (IN) transition temperatureT _IN determined by TM and LF-dielectric permittivity measurements agrees with the available data. Dielectric loss studies in the frequency region of 5–10?MHz indicate a relaxation (in the kHz region) akin to Debye type off-centered dispersion. The observed nematic relaxation is found to correspond to reorientation (about the short axis) of the nematic dipole to the external field. The temperature variation of the nematic relaxation frequencyf _R is found to follow an Arrhenius shift, with an activation energy of 1.7?eV. Temperature variation of the dielectric strength (Δε = ε _o ? ε_∞) and the distribution parameter α in the nematic phase are discussed. The dynamic response of the nematic dipoles and growth of pre-transitional fluctuations are found to be nonlinear in the vicinity of the IN transition. The value of the exponent α_eff = 0.072 indicates weak growth of transitional fluctuations across the IN transition.     

Evidence of pressure dependence tricritical point at the nematic–smectic-A transition

We examine the effect of pressure on the nematic to smectic-A N–SmA) transition within the Landau phenomenological theory. The influence of pressure on the N–SmA transition is discussed by varying the coupling between the orientational and translational order parameters. The possibility of the tricritical point at the N–SmA transition is discussed in a phenomenological way. The theoretical predictions are found to be in good qualitative agreement with experimental results.     

Algebraic Theory of Linear Viscoelastic Nematodynamics

This paper consists of two parts. The first one develops algebraic theory of linear anisotropic nematic “N-operators” build up on the additive group of traceless second rank 3D tensors. These operators have been implicitly used in continual theories of nematic liquid crystals and weakly elastic nematic elastomers. It is shown that there exists a non-commutative, multiplicative group N₆ of N-operators build up on a manifold in 6D space of parameters. Positive N-operators, which in physical applications hold thermodynamic stability constraints, do not generally form a subgroup of group N₆. A three-parametric, commutative transversal-isotropic subgroup of positive symmetric nematic operators is also briefly discussed. The special case of singular, non-negative symmetric N-operators reveals the algebraic structure of nematic soft deformation modes. The second part of the paper develops a theory of linear viscoelastic nematodynamics applicable to liquid crystalline polymer. The viscous and elastic nematic components in theory are described by using the Leslie–Ericksen–Parodi (LEP) approach for viscous nematics and de Gennes free energy for weakly elastic nematic elastomers. The case of applied external magnetic field exemplifies the occurrence of non-symmetric stresses. In spite of multi-(10) parametric character of the theory, the use of nematic operators presents it in a transparent form. When the magnetic field is absent, the theory is simplified for symmetric case with six parameters, and takes an extremely simple, two-parametric form for viscoelastic nematodynamics with possible soft deformation modes. It is shown that the linear nematodynamics is always reducible to the LEP-like equations where the coefficients are changed for linear memory functionals whose parameters are calculated from original viscosities and moduli.      

A generic equation of state for liquid crystalline phases of hard-oblate particles

A generic equation of state (EoS) is developed for the hard cylindrical disc model to describe the isotropic phase of hard cut-sphere particles introducing a correction parameter to incorporate the negative contributions from higher-order virial coefficients. The isotropic–nematic–columnar phase diagram of hard cut-sphere fluids is investigated combining the new EoS with a scaled Onsager free energy for the nematic phase and an extended cell theory for columnar phase. By mapping the virial coefficients of an oblate spherocylinder on to those of the cylindrical disc (which are known algebraically), the new generic EoS is used to describe the isotropic and nematic phases of hard oblate spherocylinder particles. The predictions of the generic EoS are compared with available simulation data.