Searcharxiv⌕ Search

arXiv subjects

Gregory M. Grason

Publications and source records attributed to Gregory M. Grason.

84 records · Page 5Linked to original sources

Continuous Crystallization in Hexagonally-Ordered Materials

We demonstrate that the phase transition from columnar-hexagonal liquid crystal to hexagonal-crystalline solid falls into an unusual universality class, which in three-dimensional allows for both discontinuous transitions as well as continuous transitions, characterized by a single set of exponents. We show by a renormalization group calculation (to first order in $ε= 4-d$) that the critical exponents of the continuous transition are precisely those of the XY model, which gives rise to a continuous evolution of elastic moduli. Although the fixed points of the present model are found to be identical to the XY model, the elastic compliance to deformations in the plane of hexagonal order, $μ$, is nonetheless shown to critically influence the crystallization transition, with the continuous transition being driven to first order by fluctuations as the in plane response grows weaker, $μ\to 0$.

cond-mat.soft↗

Structural Transitions and Soft Modes in Frustrated DNA Crystals

Relying on symmetry considerations appropriate for helical biopolymers such as DNA and filamentous actin, we argue that crystalline packings of mutually repulsive helical macromolecules fall principally into two categories: unfrustrated (hexagonal) and frustrated (rhombohedral). For both cases, we construct the Landau-Ginzburg free energy for the 2D columnar-hexagonal to 3D crystalline phase transition, including the coupling between molecular displacements {\it along} biopolymer backbone to displacements in the plane of hexagonal order. We focus on the distinct elastic properties that emerge upon crystallization of helical arrays due to this coupling. Specifically, we demonstrate that frustrated states universally exhibit a highly anisotropic in-plane elastic response, characterized by an especially soft compliance to simple-shear deformations and a comparatively large resistance to those deformations that carry the array from the low- to high-density crystalline states of DNA.

cond-mat.soft↗

Braided Bundles and Compact Coils: The Structure and Thermodynamics of Hexagonally-Packed, Chiral Filament Assemblies

Molecular chirality frustrates the two-dimensional assembly of filamentous molecules, a fact that reflects the generic impossibility of imposing a global twisting of layered materials. We explore the consequences of this frustration for hexagonally-ordered assemblies of chiral filaments that are {\it finite} in lateral dimension. Specifically, we employ a continuum-elastic description of cylindrical bundles of filaments, allowing us to consider the most general resistance to and preference for chiral ordering of the assembly. We explore two distinct mechanisms by which chirality at the molecular scale of the filament frustrates the assembly into aggregates. In the first, chiral interactions between filaments impart an overall twisting of filaments around the central axis of the bundle. In the second, we consider filaments that are inherently helical in structure, imparting a writhing geometry to the central axis. For both mechanisms, we find that a thermodynamically-stable state of dispersed bundles of {\it finite} width appears close to, but below, the point of bulk filament condensation. The range of thermodynamic stability of dispersed bundles is sensitive only to the elastic cost and preference for chiral filament packing. The self-limited assembly of chiral filaments has particular implications for a large class of biological molecules -- DNA, filamentous proteins, viruses, bacterial flagella -- which are universally chiral and are observed to form compact bundles under a broad range of conditions.

cond-mat.soft↗

Chirality and Equilibrium Biopolymer Bundles

We use continuum theory to show that chirality is a key thermodynamic control parameter for the aggregation of biopolymers: chirality produces a stable disperse phase of hexagonal bundles under moderately poor solvent conditions, as has been observed in {\it in-vitro} studies of F-actin [O. Pelletier {\it et al.}, Phys. Rev. Lett. {\bf 91}, 148102 (2003)]. The large characteristic radius of these chiral bundles is not determined by a mysterious long-range molecular interaction but by in-plane shear elastic stresses generated by the interplay between a chiral torque and an unusual, but universal, non-linear gauge term in the strain tensor of ordered chains that is imposed by rotational invariance.

cond-mat.soft↗

Phase Diagram of Chiral Biopolymer Wigner Crystals

We study the statistical mechanics of counterion Wigner crystals associated with hexagonal bundles of chiral biopolymers. We show that, due to spontaneous chiral symmetry breaking induced by frustration, these Wigner crystals would be chiral even if the biopolymers themselves were not chiral. Using a duality transformation of the model onto a "spin-charge" Hamiltonian, we show that melting of the Wigner crystal is due to the unbinding of screw dislocations and that the melting temperature has a singular dependence on the intrinsic chirality of the biopolymers. Finally, we report that, if electrostatic interactions are strongly screened, the counterions can condense in the form of an intermediate achiral Wigner solid phase that melts by the unbinding of fractional topological charges.

cond-mat.soft↗

Ordered Phases of Diblock Copolymer Micelles in Selective Solvent

We propose a mean-field model to explore the equilibrium coupling between micelle aggregation and lattice choice in neutral copolymer and selective solvent mixtures. We find both thermotropic and lyotropic transitions from face-centered cubic to body-centered cubic ordered phases of spherical micelles, in agreement with experimental observations of these systems over a broad range of conditions. Stability of the non-closed packed phase can be attributed to two physical mechanisms: the large entropy of lattice phonons near crystal melting and the preference of the inter-micelle repulsions for the body-centered cubic structure when the lattice becomes sufficiently dense at higher solution concentrations. Both mechanisms are controlled by the decrease of micelle aggregation and subsequent increase of lattice density as solvent selectivity is reduced. These results shed new light on the relationship between micelle structure -- "crewcut" or "hairy" -- and long-range order in micelle solutions.

cond-mat.soft↗

Soft Spheres Make More Mesophases

We use both mean-field methods and numerical simulation to study the phase diagram of classical particles interacting with a hard-core and repulsive, soft shoulder. Despite the purely repulsive interaction, this system displays a remarkable array of aggregate phases arising from the competition between the hard-core and shoulder length scales. In the limit of large shoulder width to core size, we argue that this phase diagram has a number of universal features, and classify the set of repulsive shoulders that lead to aggregation at high density. Surprisingly, the phase sequence and aggregate size adjusts so as to keep almost constant inter-aggregate separation.

cond-mat.soft↗

Frustrated Polyelectrolyte Bundles and T=0 Josephson-Junction Arrays

We establish a one-to-one mapping between a model for hexagonal polyelectrolyte bundles and a model for two-dimensional, frustrated Josephson-junction arrays. We find that the T=0 insulator-to-superconductor transition of the {\it quantum} system corresponds to a continuous liquid-to-solid transition of the condensed charge in the finite temperature {\it classical} system. We find that the role of the vector potential in the quantum system is played by elastic strain in the classical system. Exploiting this correspondence we show that the transition is accompanied by a spontaneous breaking of chiral symmetry and that at the transition the polyelectrolyte bundle adopts a universal response to shear.

cond-mat.soft↗

Undulated cylinders of charged diblock copolymers

We study the cylinder to sphere morphological transition of diblock copolymers in aqueous solution with a hydrophobic block and a charged block. We find a metastable undulated cylinder configuration for a range of charge and salt concentrations which, nevertheless, occurs above the threshold where spheres are thermodynamically favorable. By modeling the shape of the cylinder ends, we find that the free energy barrier for the transition from cylinders to spheres is quite large and that this barrier falls significantly in the limit of high polymer charge and low solution salinity. This suggests that observed undulated cylinder phases are kinetically trapped structures.

cond-mat.soft↗

Self-Consistent Field Theory of Multiply-Branched Block Copolymer Melts

We present a numerical algorithm to evaluate the self-consistent field theory for melts composed of block copolymers with multiply-branched architecture. We present results for the case of branched copolymers with doubly-functional groups for multiple branching generations. We discuss the stability of the cubic phase of spherical micelles, the A15 phase, as a consequence of tendency of the AB interfaces to conform to the polyhedral environment of the Voronoi cell of the micelle lattice.

cond-mat.soft↗

Interfaces in Diblocks: A Study of Miktoarm Star Copolymers

We study AB$_n$ miktoarm star block copolymers in the strong segregation limit, focussing on the role that the AB interface plays in determining the phase behavior. We develop an extension of the kinked-path approach which allows us to explore the energetic dependence on interfacial shape. We consider a one-parameter family of interfaces to study the columnar to lamellar transition in asymmetric stars. We compare with recent experimental results. We discuss the stability of the A15 lattice of sphere-like micelles in the context of interfacial energy minimization. We corroborate our theory by implementing a numerically exact self-consistent field theory to probe the phase diagram and the shape of the AB interface.

cond-mat.soft↗