Study of intrinsic anchoring in nematic liquid crystals based on modified Gruhn-Hess pair potential

A nematic liquid crystal slab composed of N molecular layers is investigated using a simple cubic lattice model, based upon the molecular pair potential which is spatially anisotropic and dependent on elastic constants of liquid crystals. A perfect nematic order is assumed in the theoretical treatment, which means the orientation of the molecular long axis coincides with the director of liquid crystal and the total free energy equals to the total interaction energy. We present a modified Gruhn-Hess model, which is relative to the splay-bend elastic constant K₁₃. Furthermore, we have studied the free nematic interfacial behavior (intrinsic anchoring) by this model in the assumption of the perfect nematic order. We find that the preferred orientation at the free interface and the intrinsic anchoring strength change with the value of modification, and that the director profile can be determined by the competition of the intrinsic anchoring with external forces present in the system. Also we simulate the intrinsic anchoring at different temperatures using Monte Carlo method and the simulation results show that the intrinsic anchoring favors planar alignment and the free interface is more disordered than the bulk.     

Lattice Boltzmann Simulation of 3D Nematic Liquid Crystal near Phase Transition

Phase transition between nematic and isotropic liquid crystal is a very weak first order phase transition.We avoid to use the normal Landau-de Gennes‘s free energy that reduces a strong first order transition,and set up a data base of free energy calculated by means of Tao-Sheng-Lin‘s extended molecular field theory that can explain the experiments of the equilibrium properties of nematic liquid crystal very well.Then we use the free energy method of lattice Boltzmann developed by Oxford group to study the phase decomposition,pattern formation in the flow of the liquid crystal near transition temperature.     

Stripe instability in thin films of smectic liquid-crystal polymers

Two-dimensional nanostripes are formed in thin films of side-chain liquid-crystalline polymer films when the material enters the smectic phase. The structure is investigated using transmission electron microscopy. Electron diffraction patterns show that the chain molecules are mostly aligned in the film plane and the average molecular director is parallel to the direction of the stripes. We discuss factors affecting the stripe amplitude and periodicity, such as the film thickness and the temperature of annealing in the nematic phase, and suggest a possible mechanism for their formation. We propose that an equilibrium instability occurs due to a competition between the layer-aligning effect of the substrate and the planar director alignment, forcing smectic layers perpendicular to the film surface. The stripes decorate the overall patterns of nematic director in the polymer film and provide a means of high-resolution imaging for observation of textures and disclinations.Received: 10 June 2003, Published online: 19 August 2003PACS: 68.37.Lp Transmission electron microscopy (TEM) (including STEM, HRTEM, etc.) - 61.30.Vx Polymer liquid crystals - 61.30.Hn Surface phenomena: alignment, anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions - 68.55.Nq Composition and phase identification     

Molecular orientation in nematic liquid crystal films with two free surfaces

The director orientation in nematic layers with two free surfaces has been studied by optical methods for different thicknesses of the film. A sharp structure transition, obtained by reducing the thickness of the film under a critical value, is reported for the first time. The same structural transition for fixed thickness is also shown to occur below a critical temperature.     

Optical Kerr effect in nematic liquid crystals: a molecular dynamics simulation study

Molecular dynamics simulations of the Gay-Berne model have been undertaken and optical response properties calculated for the isotropic and nematic phases. The components of the optical response were calculated for the coordinate system with respect to the director. Furthermore, the response for the components was separated into the orientational and collision induced contributions in order to analyse the mechanism of the optical response. It was observed, in particular, that one of the depolarized components of the response function does not vanish after long times for the nematic phase, unlike in the isotropic phase. This means that the orientation of the director can be permanently changed by instant irradiation with polarized light. The results give a microscopic picture of the optical Kerr effect in nematic liquid crystals.     

Reexamining the phase diagram of the Gay—Berne fluid

This work reexamines and updates earlier investigations on the phase behaviour of the Gay-Berne liquid crystal model, concentrating on the effect of varying temperature. Constant volume and constant pressure Monte Carlo simulations are combined for systems consisting of N = 500 molecules along different isotherms over the reduced temperature range 0.60 ≤ T ≤ 1.25. As in previous simulation studies of the model, the study identifies nematic and smectic B phases on compressing the isotropic fluid, the particular phase sequence depending on temperature. The nematic phase is found to be stable with respect to the isotropic phase for reduced temperatures T ≥ 0.75. In the temperature range 0.75 ≤ T ≤ 1.25, the phase boundaries of the isotropic-nematic transition are obtained by computing the Helmholtz free energy of both phases from thermodynamic integration. From the simulation data, the relative volume change at the isotropic-nematic transition is about 2%, and this value appears to be rather insensitive to changes in temperature. On compressing the nematic phase, the Gay-Berne fluid undergoes a strong first-order transition to the smectic B phase. This transition is studied by using constant pressure simulation, and the coexistence properties are estimated from the limits of mechanical stability of the nematic phase. Larger relative volume changes are found at the transition than those suggested by previous studies, with typical values increasing up to 10.5% as the temperature is decreased. The results are consistent with the existence of strong coupling between nematic and smectic order parameters. For temperatures T ≤ 0.70 the nematic phase is no longer stable, and the phase sequence isotropic-smectic B is observed. Therefore, the Gay-Berne model exhibits an isotropic-nematic-smectic B triple point. Extrapolating the present simulation data, this triple point is located approximately at reduced temperature T_INB ? 0.70 and reduced pressure P_INB ? 1.825.     

Tetrahedral Order in Liquid Crystals

We review the impact of tetrahedral order on the macroscopic dynamics of bent-core liquid crystals. We discuss tetrahedral order comparing with other types of orientational order, like nematic, polar nematic, polar smectic, and active polar order. In particular, we present hydrodynamic equations for phases, where only tetrahedral order exists or tetrahedral order is combined with nematic order. Among the latter, we discriminate between three cases, where the nematic director (a) orients along a fourfold, (b) along a threefold symmetry axis of the tetrahedral structure, or (c) is homogeneously uncorrelated with the tetrahedron. For the optically isotropic T_d phase, which only has tetrahedral order, we focus on the coupling of flow with, e.g., temperature gradients and on the specific orientation behavior in external electric fields. For the transition to the nematic phase, electric fields lead to a temperature shift that is linear in the field strength. Electric fields induce nematic order, again linear in the field strength. If strong enough, electric fields can change the tetrahedral structure and symmetry leading to a polar phase. We briefly deal with the T phase that arises when tetrahedral order occurs in a system of chiral molecules. To case (a), defined above, belong (i) the non-polar, achiral, optically uniaxial D2d phase with ambidextrous helicity (due to a linear gradient free energy contribution) and with orientational frustration in external fields, (ii) the non-polar tetragonal S4 phase, (iii) the non-polar, orthorhombic D2 phase that is structurally chiral featuring ambidextrous chirality, (iv) the polar orthorhombic C2v phase, and (v) the polar, structurally chiral, monoclinic C2 phase. Case (b) results in a trigonal C3v phase that behaves like a biaxial polar nematic phase. An example for case (c) is a splay bend phase, where the ground state is inhomogeneous due to a linear gradient free energy contribution. Finally, we discuss some experiments that show typical effects related to the existence of tetrahedral order. A summary and perspective is given.     

Isotropic to nematic transition of aerosil-disordered liquid crystals

We present a high-resolution study of the isotropic to nematic phase transition of a low birefringence liquid-crystal compound incorporating an aerosil gel. Calorimetry, light scattering, and microscopy data coherently combine to allow for an accurate determination of the temperature dependence of the onset of the nematic state. The nematic order develops on cooling through two distinct processes while the nematic correlation length mildly decreases. We understand the doubling of the phase transition as due to a crossover from a random-dilution regime, where the silica gel couples to the scalar part of the nematic order parameter, to a low-T random-field regime, where the coupling induces distortions in the director field.     

Molecular orientations and photorefractive effects in C60-doped liquid crystals with capillary-flow-induced alignment

Molecular orientations and photorefractive effects of C₆₀-doped nematic liquid crystals were investigated with layer-structured liquid crystal cells where a nematic phase was injected. Regardless of the surface treatments of the layers, liquid crystals injected with nematic phase showed a higher degree of director orientation and photorefractivity than those injected with an isotropic phase. The nematic alignment of liquid crystals in an untreated cell is generated by a capillary flow of liquid crystal during the nematic injection. However, it was observed that the grating formation was delayed a little longer with injection of nematic phase than with injection of isotropic phase. Received: 11 March 2002 / Revised version: 22 April 2002 / Published online: 12 July 2002     

Temperature and orientation dependence of surface relief gratings based on dye-doped polymer film with the interface of nematic liquid crystals

The formation of surface relief grating on dye-doped polymer film with the interface of nematic liquid crystals has been investigated by means of the holographic technique. The first-order diffraction efficiency of surface relief grating depends on the temperature and the orientation of molecular director in the interface of nematic liquid crystals. The diffraction efficiency is roughly independent of thermal fluctuations of molecular director in the most part of nematic temperature range and apparently drops near the transition temperature. The morphology of surface relief grating demonstrates that the surface modulation is larger for molecular director parallel to the groove direction. The experimental result also shows that the first-order diffraction efficiency is dependent on the surface modulation of surface relief grating.     

Fluctuations of orientational order in a uniaxial nematic liquid crystal with biaxial molecules and its response to an external field

Homogeneous thermal fluctuations of the orientational order parameters S and G of biaxial molecules in a uniaxial nematic liquid crystal are investigated in the framework of the molecular-statistical theory. It is demonstrated that the molecular biaxiality significantly affects the order parameters S and G, their temperature dependences in the nematic phase, the amplitude and the temperature dependence of the order parameter fluctuations in the nematic and isotropic phases, and the character of the transition from the nematic phase to the isotropic liquid phase. It is established that the fluctuations of the parameters S and G in the nematic phase are related to the temperature dependences of S and G and the susceptibilities χ_S and χ_G of the nematic liquid crystal to external fields, which leads to a change in the parameters S and G at a fixed director orientation. Explanations are offered for the known experimental data on the orientational ordering of biaxial molecules under the action of external fields in the isotropic phase of nematic liquid crystals.     

Azimuthal anchoring energy at the interface between a nematic liquid crystal and a PTFE substrate

The azimuthal anchoring energy of the nematic liquid crystal 4-pentyl-4'-cyanobiphenil (5CB) on a poly(tetrafluoroethylene) (teflon, PTFE) film is measured for the first time. The PTFE film is deposed using the Wittmann and Smith technique which consists on rubbing a bar of this polymer against a glass substrate at a controlled temperature and pressure. Measurements of the azimuthal anchoring energy are made with a reflectometric technique which provides high accuracy and sensitivity. The dependence of the azimuthal anchoring energy on temperature and on the rubbing pressure is investigated. The extrapolation length remains virtually constant in the whole temperature range of the nematic phase except for an increase of 25% close to the clearing temperature. The azimuthal anchoring energy is somewhat strong and increases with increasing the deposition pressure of PTFE. The observation of a relevant pre-transitional anisotropy of the reflection coefficients in the isotropic phase proves that the surface interactions favor an excess of orientational order. Ageing of the anchoring energy and gliding of the easy axis are experimentally observed. Both these phenomena suggest the presence of an anisotropic adsorbed layer of nematic molecules on the PTFE film.     

Free energy of semiflexible polymers and structure of interfaces

The free energy of semiflexible polymers is calculated as a functional of the compositional scalar order parameter and the orientational order parameter of second-rank tensor S_ij on the basis of a microscopic model of wormlike chains with variable segment lengths. We use a density functional theory and a gradient expansion to evaluate the entropic part of the free energy, which is given in a power series of .The interaction term of the free energy is derived with a random phase approximation. For the rigid rod limit, the nematic-isotropic transition point is given by , N and w being the degree of polymerization and the anisotropic interaction parameter, respectively, and the degree of ordering at the transition point is 0.33448. We also find that the contour length of polymer chains becomes larger in a nematic phase than in an isotropic phase. Interface profiles are obtained numerically for some typical cases. In the neighborhood of isotropic-isotropic interfaces, polymer chains tend to align parallel to the interface on the polymer-rich side and perpendicular on the poor side. When an isotropic region and a nematic region coexist, orientational order parallel to the interface is preferred in the nematic region. Received: 28 May 1998 / Revised: 12 August 1998 / Accepted: 8 September 1998     

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.     

磁场作用下向列型液晶中的分子取向短程关联

从分子统计理论的观点研究磁场对向列型液晶的作用。将向列型液晶的格胞理论推广到包含磁场作用的情况。这一理论考虑了分子取向短程关联。向列相序参数对约化温度的依赖关系和每个分子的约化内能对约化温度的依赖关系，与计算机模拟结果符合得相当好。计算了各向同性相最低过冷温度，理论结果与实验值和分子场理论的结果进行了比较。     

Strongly anisotropic elastic moduli of nematic elastomers: Analytical expressions and nonlinear temperature dependence

Exact formulae for the elastic moduli of the nematic elastomers are obtained by the implicit function method based on somewhat general energy functions. The formulae indicate that both the moduli parallel and perpendicular to the director of the nematic elastomers are smaller than the modulus of the classical elastomers because of the mechanical-nematic coupling. Moreover, the moduli are generally anisotropic due to the biaxiality induced by stretching the nematic elastomers perpendicular to the director. Then we get the explicit analytical expressions of the parallel and perpendicular moduli by making use of the Landau-de Gennes free energy and the neo-classical elastic energy. Very different from the classical elastomers, they are both strongly nonlinear functions of the temperature in the nematic phase. Furthermore, their ratio, the degree of anisotropy, changes with the temperature as well. The results agree qualitatively with some experiments. Better quantitative agreement is obtained by some modifications of the constitutive relation of the elastic energy.     

Enhancement of Nematic Order and Global Phase Diagram of a Lattice Model for Coupled Nematic Systems

We use an infinite-range Maier–Saupe model, with two sets of local quadrupolar variables and restricted orientations, to investigate the global phase diagram of a coupled system of two nematic subsystems. The free energy and the equations of state are exactly calculated by standard techniques of statistical mechanics. The nematic–isotropic transition temperature of system A increases with both the interaction energy among mesogens of system B, and the two-subsystem coupling J. This enhancement of the nematic phase is manifested in a global phase diagram in terms of the interaction parameters and the temperature T. We make some comments on the connections of these results with experimental findings for a system of diluted ferroelectric nanoparticles embedded in a nematic liquid-crystalline environment.     

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.     

Temperature dependence of the effective anchoring energy for a nematic-ferroelectric interface

Specific features of the anisotropic interaction between a nematic mixture and a polar surface of a ferroelectric triglycine sulfate crystal have been studied over a wide temperature range including the substrate's Curie point T_c. The mixture was composed of two nematic liquid crystals, 60% of p-methoxybenzylidene-p-n-butylaniline (MBBA) and 40% of p-ethoxybenzylidene-p-n-butylaniline (EBBA), and doped with a small amount of a dichroic dye. The temperature dependence of the polarized components of optical density D_j of the dye absorption band for the nematic and isotropic phases of the MBBA+EBBA mixture has been obtained using polarization optic techniques. The temperature-induced structural changes in the nematic layer near T_c were found to be related to the changes in the orientational part of the tensor order parameter Q_ik. The experimental data have been interpreted using the model, in which the dispersive van der Waals forces of the substrate stabilize the planar orientation of the nematic in the bulk competing with the short-range anchoring forces in the vicinity of T_c. At the same time, the anisotropic part of the surface energy has two terms with the orthogonal easy axes. The nature of the surface electric field and its effect on the director alignment at the interface have been clarified. Taking into account the known relation between anchoring strength and the nematic order parameter, the effective anchoring energy w_eff for the studied system has been determined as a function of temperature.     

Parameters of LC molecules’ movement measured by dielectric spectroscopy in wide temperature range

Dielectric properties of a nematic liquid crystal (NLC) mixture ZhK-1282 were investigated in the frequency range of 10²–10⁶Hz and a temperature range of ?20 to 80?°С. On the basis of the Debye’s relaxation polarization model dielectric spectra of temperature dependence of the orientational relaxation time τ and the dielectric strength δe were numerically approximated at the parallel orientation of a molecular director relative to alternating electric field. Influence of ester components in the mixture plays crucial role in relaxation processes at low temperature and external field frequency. The activation energy of the relaxation process of a rotation of molecules around their short axis was measured in a temperature interval of ?20 to ?+15?°С in which the dispersion of a longitudinal component of the dielectric constant takes place. The energy of potential barrier for polar molecules rotation in the mesophase was calculated. The value of the transition entropy from the nematic to isotropic phase was obtained from this calculation. The values of the coefficient of molecular friction and rotational diffusion were obtained by different methods. The experimental data obtained are in a satisfactory agreement with the existing theoretical models.