Non-uniformities in polymer/liquid crystal mixtures

We theoretically model the nucleation of nematic droplets during phase ordering in mixtures of a flexible polymer and a low-molecular-weight liquid crystal. By appealing to classical nucleation theory (CNT), we calculate the energy barrier to nucleation and the size of a critical nucleus. We study the influence of a metastable intermediate phase on the nucleation of the nematic. Below a triple point in the phase diagram, there are two distinct mechanisms for the formation of a nematic nucleus: 1) direct nucleation from the isotropic phase and 2) nucleation via a precursor metastable isotropic phase. We calculate the crossover concentration as a function of temperature, delineating the regions of the phase diagram in which each mechanism prevails. In the latter case, the presence of a hidden metastable isotropic-isotropic binodal may either promote or delay the nucleation of a nematic phase. Received 9 August 2002 RID="a" ID="a"e-mail: matuyama@chem.mie-u.ac.jp     

Computer simulation of heterogeneous nucleation on curved surfaces using a simplified string method combined with phase-field simulations

We show how the combination of string method with the phase-field approach can be extended from simulations of homogeneous nucleation to heterogeneous nucleation. From these simulations, it is possible to directly obtain nucleation barriers for heterogeneous nucleation on arbitrary surfaces as well as information about the size and shape of the critical nucleus. We test the method by comparing the dependence of the nucleation barrier for heterogeneous nucleation on concave and convex surfaces on the surface curvature obtained from three-dimensional phase-field simulations with predictions from classical nucleation theory and find good agreement between them.     

Solitons and defects in nematic liquid crystals under a simple shear flow and in a static external magnetic field

Under a simple shear flow and in a static external magnetic field, the production of defects in the director-aligning regime of nematic liquid crystals has been investigated in terms of the Leslie-Ericksen theory. The equation of motion of the nematic director, which conforms to the driven over-damped sine-Gordon equation, has a soliton solution of the amplitude w. We show that the stationary state with the director uniformly oriented at a Leslie angle is only a metastable state and the potential, which governs the motion of the director, has a nmnber of stable stationary states. For a strong magnetic field, the higher energy barrier between the stable and unstable states leads the director to be locked along the magnetic field direction. However, at the appropriate shear rate and magnetic field the defects, which appear as a stable solitary solution, can be nucleated from a uniformly aligned nematic liquid crystal. We have calculated the stationary travelling velocity of the solitary waves and the distance between a pair of defects.     

Dynamic Effects in Nucleation of Receptor Clusters

Nucleation theory has been widely applied for the interpretation of critical phenomena in nonequilibrium systems. Ligand-induced receptor clustering is a critical step of cellular activation. Receptor clusters on the cell surface are treated from the nucleation theory point of view. The authors propose that the redistribution of energy over the degrees of freedom is crucial for forming each new bond in the growing cluster. The expression for a kinetic barrier for new bond formation in a cluster was obtained. The shape of critical receptor clusters seems to be very important for the clustering on the cell surface. The von Neumann entropy of the graph of bonds is used to determine the influence of the cluster shape on the kinetic barrier. Numerical studies were carried out to assess the dependence of the barrier on the size of the cluster. The asymptotic expression, reflecting the conditions necessary for the formation of receptor clusters, was obtained. Several dynamic effects were found. A slight increase of the ligand mass has been shown to significantly accelerate the nucleation of receptor clusters. The possible meaning of the obtained results for medical applications is discussed.     

Phase transition in ellipsoidal droplets of nematic liquid crystals

We developed a simple method for the calculation of the director field distribution in the droplets of nematic liquid crystals (LCs) of any shape, allowing for the interaction of LCs with the droplet surface, as well as the influence of constant electric field. In contrast to different approaches, the approach that is developed in the present paper does not require any simplifying suppositions about the structure of the LC director field. The elastic-continuum theory is used, complemented with the possibility of consideration of point and linear defects. Calculations are performed using the Monte Carlo method on a simple grid. The triangulation technique is used to take the boundary conditions of droplets of a complex shape into account. The developed approach can be used for investigation of the properties of polymer-dispersed liquid crystals (PDLCs). The topological phase transitions in the nematic LC 4-cyano-4′-pentyl-biphenyl (5CB) in spherical and ellipsoidal droplets are investigated in this paper.     

Surface nucleation in the freezing of gold nanoparticles

We use molecular simulation to calculate the nucleation free energy barrier for the freezing of a 456 atom gold cluster over a range of temperatures. The results show that the embryo of the solid cluster grows at the vapor-surface interface for all temperatures studied and that the usual classical nucleation model, with the embryo growing in the core of the cluster, is unable to predict the shape of the free energy barrier. We use a simple partial wetting model that treats the crystal as a lens-shaped nucleus at the liquid-vapor interface and find that the line tension plays an important role in the freezing of gold nanoparticles.     

Rhythmic cluster generation in strongly driven colloidal dispersions

We study the response of a nematic colloidal dispersion of rods to a driven probe particle which is dragged with high speed through the dispersion perpendicular to the nematic director. In front of the dragged particle, clusters of rods are generated which rhythmically grow and dissolve by rotational motion. We find evidence for a mesoscopic cluster-cluster correlation length, independent of the imposed drag speed. Our results are based on nonequilibrium Brownian dynamics computer simulations and in line with a dynamical scaling theory.     

Trapping of a diffusing adatom by a substitutional surface defect

We propose a simple model to explain qualitatively the results of a recent field-ion-microscopy (FIM) study in which a substitutional Ir atom in the Rh(001) surface traps diffusing Rh adatoms [G.L. Kellogg, Phys. Rev. Lett., to be published]. The proposed explanation is supported by an embedded-atom-method investigation of the effect of a substitutional Pt atom in the Pd(001) surface on Pd adatom diffusion. We find a smaller energy barrier for a single adatom to diffuse around the defect than away from it, i.e., the adatom is effectively trapped by this defect in qualitative agreement with the FIM study. We also find that Pd adatom clusters are more strongly bound at the defect than away from it, indicating that such a defect can act as a nucleation site for cluster growth.     

Surface-enhanced plasmon splitting in a liquid-crystal-coated gold nanoparticle

We show that, when a gold nanoparticle is coated by a thin layer of nematic liquid crystal, the nanoparticle surface has a strong effect on the director orientation, but, surprisingly, this deformation can enhance the surface plasmon splitting. We consider three plausible liquid crystal director configurations in zero electric field: boojum pair (north-south pole configuration), baseball (tetrahedral), and homogeneous. From the discrete dipole approximation, we find that the surface plasmon splitting is largest for the boojum pair, and this result is in good agreement with experiment.     

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.     

Self-assembly and nonlinear dynamics of dimeric colloidal rotors in cholesterics

We study by simulation the physics of two colloidal particles in a cholesteric liquid crystal with tangential order parameter alignment at the particle surface. The effective force between the pair is attractive at short range and favors assembly of colloid dimers at specific orientations relative to the local director field. When pulled through the fluid by a constant force along the helical axis, we find that such a dimer rotates, either continuously or stepwise with phase-slip events. These cases are separated by a sharp dynamical transition and lead, respectively, to a constant or an ever-increasing phase lag between the dimer orientation and the local nematic director.     

Cluster dynamics and cluster size distributions in systems of self-propelled particles

Systems of self-propelled particles (SPP) interacting by a velocity alignment mechanism in the presence of noise exhibit rich clustering dynamics. Often, clusters are responsible for the distribution of (local) information in these systems. Here, we investigate the properties of individual clusters in SPP systems, in particular the asymmetric spreading behavior of clusters with respect to their direction of motion. In addition, we formulate a Smoluchowski-type kinetic model to describe the evolution of the cluster size distribution (CSD). This model predicts the emergence of steady-state CSDs in SPP systems. We test our theoretical predictions in simulations of SPP with nematic interactions and find that our simple kinetic model reproduces qualitatively the transition to aggregation observed in simulations.     

Anomalous viscoelastic response of nematic elastomers

We report a combined theoretical and experimental study of linear viscoelastic response in oriented monodomain nematic elastomers. The model predicts a dramatic decrease in the dynamic modulus in certain deformation geometries in an elastic medium with an independently mobile internal degree of freedom, the nematic director with its own relaxation dynamics. Dynamic mechanical measurements on monodomain nematic elastomers confirm our predictions of dependence on shear geometry and on nematic order, and also show a very substantial mechanical loss clearly associated with director relaxation.     

Critical voltages and blocking stresses in nematic gels

We present a model of the dynamics of director rotation in nematic gels under combined electro-mechanical loading. Focusing on a model specimen, we describe the critical voltages that must be exceeded to achieve director reorientation, and the blocking stresses that prevent alignment of the nematic director with the applied electric field. The corresponding phase diagram shows that the dynamic thresholds defined above are different from those predicted on the sole basis of energetics. Multistep loading programs are used to explore the energy landscape of our model specimen, showing the existence of multiple local minima under the same voltage and applied stress. This leads us to conclude that hysteresis should be expected in the electro-mechanical response of nematic gels.     

Nucleation on a sphere: the roles of curvature,confinement and ensemble

ABSTRACT

By combining Monte Carlo simulations and analytical models, we demonstrate and explain how the gas-to-liquid phase transition of colloidal systems confined to a spherical surface depends on the curvature and size of the surface, and on the choice of thermodynamic ensemble. We find that the geometry of the surface affects the shape of the free energy profile and the size of the critical nucleus by altering the perimeter–area ratio of isotropic clusters. Confinement to a smaller spherical surface results in both a lower nucleation barrier and a smaller critical nucleus size. Furthermore, the liquid domain does not grow indefinitely on a sphere. Saturation of the liquid density in the grand canonical ensemble and the depletion of the gas phase in the canonical ensemble lead to a minimum in the free energy profile, with a sharp increase in free energy for additional growth beyond this minimum.     

Emergent biaxiality in nematic microflows illuminated by a laser beam

Anisotropic fluids (e.g. liquid crystals) offer a remarkable promise as optofluidic materials owing to the directional, tunable, and coupled interactions between the material, flow, and the optical fields. Here we present a comprehensive in silico treatment of this anisotropic interaction by performing nonequilibrium molecular dynamics simulations. We quantify the response of a nematic liquid crystal (NLC) undergoing a Poiseuille flow in the Stokes regime, while being illuminated by a laser beam incident perpendicular to the flow direction. We adopt a minimalistic model to capture the interactions, accounting for two features: first, the laser heats up the NLC locally; and second, the laser polarises the NLC and exerts an optical torque that tends to reorient molecules of the nematic phase. Because of this reorientation the liquid crystal exhibits small regions of biaxiality, where the nematic director is one symmetry axis and the axis of rotation for the reorientation of the molecules is the other one. We find that the relative strength of the viscous and the optical torques mediates the flow-induced response of the biaxial regions, thereby tuning the emergence, shape and location of the regions of enhanced biaxiality. The mechanistic framework presented here promises experimentally tractable routes toward novel optofluidic applications based on material-flow-light interactions.     

Biaxial nematic phase in a thermotropic liquid-crystalline side-chain polymer

We report on variable-angle deuterium NMR measurements of nematic liquid-crystalline side-chain polymers, where we have found proof of the existence of a biaxial nematic phase in a system with a side-on attachment of the mesogenic group to the polymer backbone. This provides efficient coupling to the polymer backbone and thus stabilizes the as yet elusive biaxial phase. The experimental approach is validated on a uniaxial end-on nematic polymer, and the reliability of the results is investigated in detail using two-dimensional correlation spectra, providing information on director distribution effects.     

Collective effects in doped nematic liquid crystals

We studied the collective elastic interaction in a system of many macroparticles embedded in a nematic liquid crystal. A theoretical approach to the interaction of macroparticles via deformation of the director field [1] is developed. It is found that the director field distortion induced by many particles leads to the screening of the elastic pair interaction potential. This screening strongly depends on the shape of the embedded particles: it exists for anisotropic particles and is absent for spherical ones. Our results are valid for the homeotropic and the planar anchoring on the particle surface and for different Frank constants. We apply our results to cylindrical particles in a nematic liquid crystal. In a system of magnetic cylindrical grains suspended in a nematic liquid crystal, the external magnetic field perpendicular to the grain orientation results in inclining the grains to the director and induces an elastic Yukawa-law attraction between the grains. The appearance of this elastic attraction can explain the cellular texture in magnetically doped liquid crystals in the presence of the magnetic field [2].