Transition pathways connecting crystals and quasicrystals.

Due to structural incommensurability, the emergence of a quasicrystal from a crystalline phase represents a challenge to computational physics. Here, the nucleation of quasicrystals is investigated by using an efficient computational method applied to a Landau free-energy functional. Specifically, transition pathways connecting different local minima of the Lifshitz-Petrich model are obtained by using the high-index saddle dynamics. Saddle points on these paths are identified as the critical nuclei of the 6-fold crystals and 12-fold quasicrystals. The results reveal that phase transitions between the crystalline and quasicrystalline phases could follow two possible pathways, corresponding to a one-stage phase transition and a two-stage phase transition involving a metastable lamellar quasicrystalline state, respectively.

Construction of a Pathway Map on a Complicated Energy Landscape.

How do we search for the entire family tree of possible intermediate states, without unwanted random guesses, starting from a stationary state on the energy landscape all the way down to energy minima? Here we introduce a general numerical method that constructs the pathway map, which guides our understanding of how a physical system moves on the energy landscape. The method identifies the transition state between energy minima and the energy barrier associated with such a state. As an example, we solve the Landau-de Gennes energy incorporating the Dirichlet boundary conditions to model a liquid crystal confined in a square box; we illustrate the basic concepts by examining the multiple stationary solutions and the connected pathway maps of the model.

Elastic properties of liquid-crystalline bilayers self-assembled from semiflexible-flexible diblock copolymers.

The mechanical response and shape of self-assembled bilayer membranes depend crucially on their elastic properties. Most of the studies focused on the elastic properties of fluid membranes, despite the ubiquitous presence of membranes with liquid-crystalline order. Here the elastic properties of liquid-crystalline bilayers self-assembled from diblock copolymers composed of a semiflexible block are studied theoretically. Specifically, the self-consistent field theory (SCFT) is applied to a model system composed of semiflexible-flexible diblock copolymers dissolved in flexible homopolymers that act as solvents. The free energy of self-assembled tensionless bilayer membranes in three different geometries, i.e. planar, cylindrical and spherical, is obtained by solving the SCFT equations using a hybrid method, in which the orientation-dependent functions are treated using the spherical harmonics, whereas the position-dependent operators are treated using the compact difference schemes. The bending modulus κM and Gaussian modulus κG of the bilayer are extracted from the free energies. The effects of the molecular parameters of the system, such as the chain rigidity and the orientational interaction, are systematically examined.

Formation of three-dimensional colloidal crystals in a nematic liquid crystal.

We investigate the possible structures of three-dimensional colloidal crystals formed when these spherical particles are dispersed in a liquid crystal. The case of a strong homeotropic boundary condition is considered here. Their corresponding defect structures in the space-filler nematic liquid crystal are induced by the presence of the spherical surface of the colloids and produce an attraction between colloidal particles. Here, a standard Landau-de Gennes free energy model for a spatially inhomogeneous liquid crystal is numerically minimized to yield an optimal configuration of both spherical colloids and the orientational field. The stable and metastable structures obtained in this work are described and analyzed according to the type of periodic liquid-crystal defect lines that couple the colloidal spheres together. A large range of the spherical size is covered in this study, corresponding to a 5CB-liquid-crystal comparison for assembling micron- to nano-sized colloidal spheres. Multiple configurations are found for each given particle size and the most stable state is determined by a comparison of the free energies. From large to small colloidal particles, a sequence of structures, which range from quasi-one-dimensional (columnar), to quasi-two-dimensional (planar), and to truly three-dimensional, are found to exist.

Liquid crystalline bilayers self-assembled from rod-coil diblock copolymers.

The structure and phase behaviour of bilayer membranes self-assembled from rod-coil diblock copolymers are studied using the self-consistent field theory, focusing on the occurrence and relative stability of liquid crystalline phases induced by the geometric shape and orientational interaction of the rod-blocks. A variety of liquid crystalline bilayers, corresponding to the smectic phases in bulk systems, are predicted to occur as equilibrium phases of the system. The ordered morphologies and phase behaviour of the system are analyzed. Phase diagrams of the self-assembled bilayers are constructed. The theoretical results provide an understanding of the formation mechanisms of these intricate phases.

Nematic ordering of semiflexible polymers confined on a toroidal surface.

We study the isotropic-like and nematic states of wormlike liquid-crystal polymers embedded on the surface of a torus. The role played by surface curvature, which couples to the molecular rigidity, is reported as the main reason that causes the weak nematic ordering in an otherwise ordinary isotropic phase. The same coupling has a profound effect on the nematic states as well, which are stabilized by the Onsager excluded-volume interaction; the latter has been frequently used to study lyotropic liquid crystal polymers and is used here as an example of the physical mechanisms that drive the system to make orientational ordering. We identify important parameters in the system which are used as axes of the four-dimensional phase diagram. The numerical study demonstrates a strong correlation between the liquid-crystal defect-free and defect structures and the geometry of the liquid-crystal embedded surface.

Surface-induced phase transitions of wormlike chains in slit confinement.

On the basis of a self-consistent field theory treatment of semi-flexible polymer chains, we analyze the effects of the flexibility on the structure of polymers sterically confined between two parallel, structureless walls separated by a distance. The model is built from a wormlike chain formalism which crosses over from the rod limit to the flexible limit, and the Onsager-type interaction which describes the orientation-dependent excluded-volume interaction. Three surface states were obtained from the numerical solution to the theory: uniaxial, biaxial, and condensed. As the overall density increases in such a lyotropic system, first order phase transitions between uniaxial and biaxial states, biaxial and condensed states can occur.

Conformation of polyelectrolytes in poor solvents: variational approach and quantitative comparison with scaling predictions.

We present the results of variational calculations of a polyelectrolyte solution with low salt in poor solvent conditions for a polymer backbone. By employing the variation method, we quantitatively determined the diagram of the state of the polyelectrolyte in poor solvents as a function of the charge density and the molecular weight. The exact structure and diagram of the polyelectrolyte were compared to the scaling predictions of the necklace model developed by Dobrynin and Rubinstein [Prog. Polym. Sci. 30, 1049-1118 (2005); Dobrynin and Rubinstein, Macromolecules 32, 915-922 (1999); Dobrynin and Rubinstein, Macromolecules 34, 1964-1972 (2001)]. We find that the scaling necklace model may be used as a rather good estimation and analytical approximation of the exact variational model. It is also pointed out that the molecular connection of polymer is crucial for ellipsoid and necklace conformation.

Is there a third order phase transition for supercritical fluids?

We prove that according to Molecular Dynamics (MD) simulations of liquid mixtures of Lennard-Jones (L-J) particles, there is no third order phase transition in the supercritical regime beyond Andrew's critical point. This result is in open contrast with recent theoretical studies and experiments which instead suggest not only its existence but also its universality regarding the chemical nature of the fluid. We argue that our results are solid enough to go beyond the limitations of MD and the generic character of L-J models, thus suggesting a rather smooth liquid-vapor thermodynamic behavior of fluids in supercritical regime.

Rigid linear particles confined on a spherical surface: phase diagram of nematic defect states.

A thin film of liquid crystal confined on a spherical surface displays topological defects, as demonstrated by experimental observation of micron-sized double-emulsion droplets. Proposals have been made in practical applications to design novel materials by using these patterned textures. Recent phenomenological models and Monte Carlo computer simulations revealed organized defect structures with different characteristics. Here, we theoretically investigate the structure of the nematic ordering resulted from the excluded-volume interaction between rigid molecules confined on a spherical surface. The free-energy model follows a basic idea originally proposed by Onsager for studying a nematic fluid made of rigid particles. We tackle this fundamental model numerically to produce high-precision free-energy branches that enable structural determination.

Modified diffusion equation for the wormlike-chain statistics in curvilinear coordinates.

One of the essential physical quantities used to study the conformation and structure of polymers is the so-called propagator in polymer theories. On the basis of the wormlike-chain statistical-physics model, we derive the partial diffusion equation that the propagator satisfies, for a curvilinear coordinate system. As it turns out, an additional term exists, that couples the rotating local coordinate frame with an orientation differential operator; this term has not been previously documented. In addition, for a wormlike chain moving on a curved surface, the external-field term needs to be supplemented by a surface curvature energy penalty.

On the existence of a third-order phase transition beyond the Andrews critical point: a molecular dynamics study.

The possibility of the existence of a gas-liquid third order phase transition for fluids is becoming a subject of growing interest. Experimental work suggests its existence for specific systems while recent theoretical models claim its universality. In this work, we employ Molecular Dynamics and investigate the third-order phase transition beyond the Andrews critical point by treating a system of Lennard-Jones particles along three isotherms. Two partial derivatives of the Gibbs free energy are measured, namely the molar constant pressure heat capacity and isothermal compressibility. The convergence of these simulations with respect to the system size as well as the cut-off radius is carefully checked. The obtained results show that partial derivatives certainly do not present sharp cusp singularities at the maxima, and actually suggest that there are no singularities at all. On these basis we then conclude that a third-order phase transition in the considered temperature region: T∗ ≥ 1.36 may indeed not exist.

Effect of exposure to trace elements in the soil on the prevalence of neural tube defects in a high-risk area of China.

OBJECTIVE: Our objective is to build a model that explains the association between the exposure to trace elements in the soil and the risk of neural tube defects. METHODS: We built a function with different parameters to describe the effects of trace elements on neural tube defects. The association between neural tube defects and trace element levels was transformed into an optimization problem using the maximum likelihood method. RESULTS: Tin, lead, nickel, iron, copper, and aluminum had typical layered effects (dosage effects) on the prevalence of neural tube defects. Arsenic, selenium, zinc, strontium, and vanadium had no effect, and molybdenum had one threshold value that affected the prevalence of birth defects. CONCLUSION: As an exploratory research work, our model can be used to determine the direction of the effect of the trace element content of cultivated soil on the risk of neural tube defects, which shows the clues by the dosage effect of their toxicological characteristics. Based on our findings, future biogeochemical research should focus on the direct effects of trace elements on human health.

Nucleation of ordered phases in block copolymers.

Nucleation of various ordered phases in block copolymers is studied by examining the free-energy landscape within the self-consistent field theory. The minimum energy path (MEP) connecting two ordered phases is computed using a recently developed string method. The shape, size, and free-energy barrier of critical nuclei are obtained from the MEP, providing information about the emergence of a stable ordered phase from a metastable phase. In particular, structural evolution of embryonic gyroid nucleus is predicted to follow two possible MEPs, revealing an interesting transition pathway with an intermediate perforated layered structure.

Numerical simulation of phase separation coupled with crystallization.

The kinetics of liquid-liquid phase separation and polymer crystallization observed in double-quench experiments with blends of poly(ethylene-co-hexene) and poly(ethylene-co-butene) are studied using time-dependent Ginzburg-Landau Model. Numerical simulations demonstrate that our model can successfully reproduce three experimental phenomena: The decrease in number and size of crystallized spherulites with increasing time in phase separation, the preponderance of nuclei near the domain interface, and the subphase separation and subcrystallization occurring when the second quench is very deep. Moreover, the simulations are consistent with the recently proposed mechanism of "phase separation fluctuation assisted nucleation" in the crystallization process.

Continuum theory of a moving membrane.

We derive a set of equations for the dynamics of evolving fluid membranes, such as cell membranes, in the presence of bulk fluids. We model the membrane as a surface endowed with a director field, which describes the local average orientation of the molecules on the membrane. A model for the elastic energy of a surface endowed with a director field is derived using liquid crystal theory. This elastic energy reduces to the well-known Helfrich energy in the limit when the directors are constrained to be normal to the surface. We then derive the full dynamic equations for the membrane that incorporate both the elastic and viscous effects, with and without the presence of bulk fluids. We also consider the effect of local spontaneous curvature, arising from the presence of membrane proteins. Overall, the systems of equations allow us to carry out stable, accurate, and robust numerical modeling for the dynamics of the membranes.

Stability of icosahedral quasicrystals in a simple model with two-length scales.

The phase behaviour of a free energy functional with two length scales is examined by comparing the free energy of different candidate phases including three-dimensional icosahedral quasicrystals. Accurate free energy of the quasicrystals has been obtained using the recently developed projection method. The results reveal that the icosahedral quasicrystal and body-centred-cubic spherical phase are the stable ordered phases of the model. Furthermore, the difference between the results obtained from the projection method and the one-mode approximation has been analyzed in detail. The present study extends previous results on two-dimensional systems, demonstrating that the interactions between density waves at two length scales can stabilize two- and three-dimensional quasicrystals.

Topological defects in an unconfined nematic fluid induced by single and double spherical colloidal particles.

We present numerical solutions to the Landau-de Gennes free-energy model under the one-constant approximation for systems of single and double spherical colloidal particles immersed in an otherwise uniformly aligned nematic liquid crystal. A perfect homeotropic surface anchoring of liquid-crystal molecules on the spherical surface is considered. A large parameter space is carefully examined, including those in the free-energy model and those describing the dimer configurations and the background liquid-crystal orientation. The stability of the resulting liquid-crystal defects appearing in the neighborhood of the colloidal dimer pair is analyzed in light of the numerical results for their free energies. A number of scenarios are considered: a free dimer pair in a nematic fluid where the free-energy ground states are described in terms of a phase diagram, and a constrained dimer pair where the interparticle distance and the relative orientation of the distance vector to the nematic director can be manipulated. We pay particular attention to the nonsymmetric solutions, which yield several metastable defect states that can be observed in real systems. The high-precision numerical calculations are based on a spectral method, which is an enabling factor that allows us to compare the subtle difference in the free energies of different defect structures.

Modified models of polymer phase separation.

In this paper we discuss continuum models of phase separation in polymer solutions, with emphasis on the thermodynamic foundation of these models. We demand that these models obey a free energy dissipation relation, which in the present context plays the role of the second law of thermodynamics, since the system is isothermal. First, we derive a modified two-fluid model for viscoelastic phase separation from nonequilibrium thermodynamics. Then we study the special case when only diffusion is present, and hydrodynamic effects are neglected. Numerical results demonstrate that our models show better stability properties and at the same time reproduce the expected physical phenomena such as volume shrinking and phase inversion. Our findings suggest that these important phenomena are caused by a diffusional asymmetry of the constituent molecules.

Stability of two-dimensional soft quasicrystals in systems with two length scales.

The relative stability of two-dimensional soft quasicrystals in systems with two length scales is examined using a recently developed projection method, which provides a unified numerical framework to compute the free energy of periodic crystal and quasicrystals. Accurate free energies of numerous ordered phases, including dodecagonal, decagonal, and octagonal quasicrystals, are obtained for a simple model, i.e., the Lifshitz-Petrich free-energy functional, of soft quasicrystals with two length scales. The availability of the free energy allows us to construct phase diagrams of the system, demonstrating that, for the Lifshitz-Petrich model, the dodecagonal and decagonal quasicrystals can become stable phases, whereas the octagonal quasicrystal stays as a metastable phase.