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The Gay–Berne (GB) potential has proved highly successful in the simulation of liquid crystal phases, although it is fairly demanding in terms of resources for simulations of large (e.g., N>105) systems, as increasingly required in applications. Here, we introduce a soft-core GB model, which exhibits both liquid crystal phase behavior and rapid equilibration. We show that the Hamiltonian replica exchange method, coupled with the newly introduced soft-core GB model, can effectively speed up the equilibration of a GB liquid crystal phase by frequent exchange of configurations between replicas, while still recovering the mesogenic properties of the standard GB potential. [ABSTRACT FROM AUTHOR]

We perform model calculations of the macroscopic diffusion coefficient for a solute moving in a chiral nematic (cholesteric) liquid crystal (LC) phase applying the methodology developed by Frezzato et al. [J. Chem. Phys. 122, 164904 (2005)]. Three types of solutes with different features are studied: ellipsoid [roto-translational coupling (RTC) absent], bent rod (RTC present), and two-blade propeller (with RTC and chiral shape). For each prototype molecule we estimate the effect of cholesteric helix pitch and local order on the diffusion along the helix axis. For the ellipsoidal particle we find that translational diffusion is slowed down by rotation around the short axis. For the chiral solute we show that the enantiomer with shape chirality opposite to that of the LC phase is slowed down more than the other. This provides a proof of principle of the possibility of separating the two enantiomers via transport in a suitable chiral medium. [ABSTRACT FROM AUTHOR]

We present a nonperturbative solution of the rotational diffusion equation for an asymmetric rotor reorienting in a uniaxial liquid crystal, such as a nematic, smectic A or membrane bilayer covering the full range of order parameters from isotropic to complete order for rod-like and plate-like molecules. We obtain explicit expressions for the rotational diffusion matrix elements for a potential containing arbitrary rank interactions. For the actual numerical computations we consider the rotor with biaxial diffusion tensor to be subject to a second rank biaxial orienting potential. We study in detail the influence of changes in diffusion tensor and ordering matrix biaxiality on correlation functions and correlation times of first and second rank and we comment on experiments that can be sensitive to biaxiality effects in the diffusion tensor. We give a comparison with approximate results that have appeared in the literature. [ABSTRACT FROM AUTHOR]

A Monte Carlo method for studying anisotropic systems with a new type of boundary conditions is proposed. The missing interactions at the sample box surface are replaced by interactions with ghost molecules. The orientations of these ghost particles are sampled from a ‘‘least biased’’ singlet distribution obtained self-consistently from the order parameter inside the sample. The method is tested on the Lebwohl–Lasher model with 125 and 1000 particles. Results for the transition temperature and order parameters are in good agreement with those obtained from simulation of much larger systems. The method is fairly general and should be applicable in a variety of simulations. Here we show that it can also be used to study director fluctuations in nematogen models. [ABSTRACT FROM AUTHOR]

Lattice dynamical calculations of undoped and doped polyparaphenylene are carried out and the results compared with the vibrational spectra presently available in the literature. The purpose of the work is to determine from vibrational spectra the extent of delocalization of π electrons along the chain. Moreover, it is suggested that the doping induced spectra are consistent with the formation of bipolarionic type defects. [ABSTRACT FROM AUTHOR]

We have investigated with extensive Monte Carlo simulations in the isothermal isobaric ensemble a system of N=8192 elongated attractive-repulsive biaxial Gay-Berne (GB) particles. We have found uniaxial and biaxial nematic phases and a biaxial orthogonal smectic phase in this thermotropic model system. © 2000 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We investigate the switching of a biaxial nematic filling a flat cell with planar homogeneous anchoring using a coarse-grained molecular dynamics simulation. We have found that an aligning field applied across the film, and acting on specific molecular axes, can drive the reorientation of the secondary biaxial director up to one order of magnitude faster than that for the principal director. While the π/2 switching of the secondary director does not affect the alignment of the long molecular axes, the field-driven reorientation of the principal director proceeds via a concerted rotation of the long and transversal molecular axes. More importantly, while upon switching off a (relatively) weak or intermediate field, the biaxial nematic liquid crystal is always able to relax to the initial surface aligned director state; this is not the case when using fields above a certain threshold. In that case, while the secondary director always recovers the initial state, the principal one remains, occasionally, trapped in a nonuniform director state due to the formation of domain walls. [ABSTRACT FROM AUTHOR]

We study by means of virtual molecular dynamics computer experiments the response of a bulk biaxial nematic to an applied external field and, in particular, the relative speed of reorientation of the principal director axis and of the secondary one, typical of these new materials, upon a π/2 field switch. We perform the simulations setting up and integrating the equations of motion for biaxial Gay-Berne particles using quaternions and a suitable time reversible symplectic integrator. We find that switching of the secondary axis is up to an order of magnitude faster than that of the principal axis, and that under fields above a certain strength a reorganization of local domains, temporarily disrupting the nematic and biaxial ordering, rather than a collective concerted reorientation occurs. [ABSTRACT FROM AUTHOR]

The possibility of using cholesteric phases for discriminating enantiomers of a chiral solute on the basis of their different transport properties, motivates the investigation of the translational diffusion by taking fully into account the roto-translational coupling. In this article a detailed theoretical analysis is presented for the transport properties evaluated according to the asymptotic limit of the mean-squared displacement. A general relation is derived for the transport coefficients, having as main ingredients the mean-field potential due to the mesophase, and the diffusion tensor with its purely translational and rotational components, and with the blocks describing the roto-translational coupling. The application of the theory to nematic phases shows that the roto-translational coupling generates a dynamical contribution reducing the transport coefficients evaluated by taking into account only the translational diffusion components in the center of diffusion. The theory is also specialized to a cholesteric phase with a given helical pitch for the director arrangement, in a form which is suitable for calculations of model systems of chiral solutes to be presented in a forthcoming paper. [ABSTRACT FROM AUTHOR]

We study the relation between the chirality of a discotic mesogen and that of the chiral columnar aggregates that they can spontaneously form by self-assembly. We discuss first the different types of chiral columns that can be in principle obtained. We introduce then a simple two-site Gay–Berne dissymmetric molecular model where chirality can be easily varied and perform extensive NPT Monte Carlo simulations of samples of these particles for different chiralities. At low temperatures we find nematic discotic and columnar mesophases formed by overall chiral columns and we analyze the results in terms of suitably defined observables and chiral correlation functions. We find that, at least for our model system, the columnar chirality is not originating from a regular helical or spiral arrangement of particles but it is mainly due to one-particle high-chirality defects separated by low-chirality domains. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We discuss the reorientation of a cylindrically symmetric probe in a biaxial orthorombic medium, such as a biaxial nematic. We write down and solve for the first time the rotational diffusion equation for a rod-like or disc-like uniaxial probe reorienting in a medium of biaxial symmetry. We calculate first and second rank correlation functions both in the uniaxial and biaxial phase, giving the possibility of following the evolution of dynamic observables of interest (e.g. spectral densities) through the uniaxial–biaxial phase transition. Nonperturbative and approximate analytical solutions are provided. [ABSTRACT FROM AUTHOR]

We present a computational approach to model hole transport in an amorphous semiconducting fluorene-triphenylamine copolymer (TFB), which is based on the combination of molecular dynamics to predict the morphology of the oligomeric system and Kinetic Monte Carlo (KMC), parameterized with quantum chemistry calculations, to simulate hole transport. Carrying out a systematic comparison with available experimental results, we discuss the role that different transport parameters play in the KMC simulation and in particular the dynamic nature of positional and energetic disorder on the temperature and electric field dependence of charge mobility. It emerges that a semi-quantitative agreement with experiments is found only when the dynamic nature of the disorder is taken into account. This study establishes a clear link between microscopic quantities and macroscopic hole mobility for TFB and provides substantial evidence of the importance of incorporating fluctuations, at the molecular level, to obtain results that are in good agreement with temperature and electric field-dependent experimental mobilities. Our work makes a step forward towards the application of nanoscale theoretical schemes as a tool for predictive material screening. [ABSTRACT FROM AUTHOR]

The NMR spectrum of n-hexane orientationally ordered in the nematic liquid crystal ZLI-1132 is analysed using covariance matrix adaptation evolution strategy (CMA-ES). The spectrum contains over 150 000 transitions, with many sharp features appearing above a broad, underlying background signal that results from the plethora of overlapping transitions from the n-hexane as well as from the liquid crystal. The CMA-ES requires initial search ranges for NMR spectral parameters, notably the direct dipolar couplings. Several sets of such ranges were utilized, including three from MD simulations and others from the modified chord model that is specifically designed to predict hydrocarbon-chain dipolar couplings. In the end, only inaccurate dipolar couplings from an earlier study utilizing proton-proton double quantum 2D-NMR techniques on partially deuterated n-hexane provided the necessary estimates. The precise set of dipolar couplings obtained can now be used to investigate conformational averaging of n-hexane in a nematic environment. [ABSTRACT FROM AUTHOR]

We report the results of atomistic molecular dynamics simulations of 4-n-octyl-4′ cyanobiphenyl (8CB) on samples of 750 and 3000 molecules showing the spontaneous formation of the nematic phase and then of smectic layers by gradually cooling down from the isotropic phase. Orientational, positional, and mixed order parameters, layer spacing, translational diffusion tensor components and their temperature dependence are reported. A detailed comparison with available experimental data validates the model and force field employed and clarifies the molecular organization of this important liquid crystal often used as reference smectic material. [ABSTRACT FROM AUTHOR]

Classical molecular dynamics simulations have been used to explore the phase diagrams for a family of attractive-repulsive soft-core Gay-Berne models [R. Berardi, C. Zannoni, J. S. Lintuvuori, and M. R. Wilson, J. Chem. Phys. 131, 174107 (2009)] and determine the effect of particle softness, i.e., of a moderately repulsive short-range interaction, on the order parameters and phase behaviour of model systems of uniaxial and biaxial ellipsoidal particles. We have found that isotropic, uniaxial, and biaxial nematic and smectic phases are obtained for the model. Extensive calculations of the nematic region of the phase diagram show that endowing mesogenic particles with such soft repulsive interactions affect the stability range of the nematic phases, and in the case of phase biaxiality it also shifts it to lower temperatures. For colloidal particles, stabilised by surface functionalisation, (e.g., with polymer chains), we suggest that it should be possible to tune liquid crystal behaviour to increase the range of stability of uniaxial and biaxial phases (by varying solvent quality). We calculate second virial coefficients and show that they are a useful means of characterising the change in effective softness for such systems. For thermotropic liquid crystals, the introduction of softness in the interactions between mesogens with overall biaxial shape (e.g., through appropriate conformational flexibility) could provide a pathway for the actual chemical synthesis of stable room-temperature biaxial nematics. [ABSTRACT FROM AUTHOR]

The aggregation of liquid crystal nanodroplets from a homogeneous solution is an important but not well understood step in the preparation of various advanced photonic materials. Here, the authors performed molecular dynamics computer simulations of the formation of liquid crystalline nanodroplets, starting from an isotropic and uniform binary solution of spherical Lennard-Jones (solvent) and elongated ellipsoidal Gay-Berne (solute) rigid particles in low (<10%) concentration. They studied the dynamics of demixing and the mesogen ordering process and characterized the resulting nanodroplets assessing the effect of temperature, composition, and specific solute-solvent interaction on the morphology, structure, and anisotropy. They find that the specific solute-solvent interaction, composition, and temperature can be adjusted to tune the nanodroplet growth and size. [ABSTRACT FROM AUTHOR]

The orientational order parameters and conformational behavior of five relatively large rodlike molecules, biphenyl, trans-stilbene, 1,3-diphenyl-butadiene, 1,3,5-diphenyl-hexatriene, and 1,3,5,7-diphenyl-octatetraene, dissolved in the thermotropic liquid crystal ZLI-1167, have been studied using an integrated approach combining 13C NMR measurements and quantum mechanical computations of carbon chemical shift tensors. Besides biphenyl, the phenyl moiety of all structures has been found to have a high rotational mobility in the temperature range of the present experiments. The rank-two order parameter in the nematic phase is found to increase steadily from the shortest to the longest term of the series at any temperature within the nematic range. The molecular biaxiality order parameter is found to be small and essentially constant with temperature, giving further support to the common assumption of effective uniaxiality for these probes [ABSTRACT FROM AUTHOR]

Liquid crystal phases formed by bent-shaped (or “banana”) molecules are currently of great interest. Here we investigate by Monte Carlo computer simulations the phases formed by rigid banana molecules modeled combining three Gay-Berne sites and containing either one central or two lateral and transversal dipoles. We show that changing the dipole position and orientation has a profound effect on the mesophase stability and molecular organization. In particular, we find a uniaxial nematic phase only for off-center dipolar models and tilted phases only for the one with terminal dipoles. [ABSTRACT FROM AUTHOR]

We apply a Monte Carlo polymerization model for Gay-Berne [J. Chem. Phys. 74, 3316 (1981)] monomers that we have recently introduced [J. Chem. Phys. 121, 9123 (2004)] to investigate with computer simulations the effects of nanoconfinement and anchoring type on the structure of the main-chain liquid-crystal polymers formed in thin films, in the presence of several types of surface alignment: parallel to the interface (random and uniform) or perpendicular to it (homeotropic). We perform first a study of the confined monomers and then we examine the features of the polymer chains obtained from an isotropic or nematic sample. We find a significant effect of the anchoring conditions on the characteristics of the chains and particularly striking differences between planar and homeotropic boundaries. Furthermore, our results indicate that the choice of different anchorings could be used to tune the linearity and degree of polymerization of the chains. [ABSTRACT FROM AUTHOR]

We discuss the problem of roto-translational diffusion of a rigid biaxial molecule dissolved in a uniaxial smectic liquid crystal phase. We examine distorted rod and disklike molecules and show how biaxiality and roto-translational coupling can produce significant effects on some of the correlation functions and spectral densities most useful in analyzing experimental observables. © 2000 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We present a simple molecular level model based on Gay-Berne monomers linked by finitely extendable nonlinear elastic potential bonds for describing main chain polymerization in liquid crystals. We apply the model to study the influence that the order of the medium has on the characteristics of the chains obtained. We find that the chains prepared from the nematic are actually straighter than those obtained from a polymerization in the isotropic phase and that they are characterized by a small number of hairpins as experimentally observed. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The statistical principle of maximum entropy is applied to the analysis of dipolar couplings from 1H NMR of nonrigid molecules dissolved in liquid-crystalline phases. A distribution function for the orientational and inter-ring angles is so obtained. The most probable internal angle φ is determined for 4,4’-dichlorobiphenyl (φ=34°) in the nematic phase of I52, 4-pentyl-4’-cyanobiphenyl (φ=32°) and 4’-Br-4-Cl-2,6-difluorobiphenyl (φ=42°) in EBBA. The physical reliability of the distributions determined is discussed. The maximum-entropy treatment seems to indicate a limit for the information on the internal motion obtainable from the experimental data. [ABSTRACT FROM AUTHOR]

The NMR spectra of n-pentane as solute in the liquid crystal 5CB are measured at several temperatures in the nematic phase. Atomistic molecular dynamics simulations of this system are carried out to predict the dipolar couplings of the orientationally ordered pentane, and the spectra predicted from these simulations are compared with the NMR experimental ones. The simulation predictions provide an excellent starting point for analysis of the experimental NMR spectra using the covariance matrix adaptation evolutionary strategy. This shows both the power of atomistic simulations for aiding spectral analysis and the success of atomistic molecular dynamics in modeling these anisotropic systems. [ABSTRACT FROM AUTHOR]