60 research outputs found
Effective interaction between star polymers
The distance-resolved effective interaction between two star polymers in a
good solvent is calculated by Molecular Dynamics computer simulations. The
results are compared with a pair potential proposed recently by Likos et al.
[Phys. Rev. Lett. 1998, 80, 4450] which is exponentially decaying for large
distances and crosses over, at the corona diameter of the star, to an ultrasoft
logarithmic repulsion for small distances. Excellent agreement is found in a
broad range of star arm numbers.Comment: final version as published, 9 pages + 5 ps-figure
Fluid and solid phases of the Gaussian core model
We study the structural and thermodynamic properties of a model of point
particles interacting by means of a Gaussian pair potential first introduced by
Stillinger [Stillinger F H 1976 J. Chem. Phys. 65, 3968]. By employing integral
equation theories for the fluid state and comparing with Monte Carlo simulation
results, we establish the limits of applicability of various common closures
and examine the dependence of the correlation functions of the liquid on the
density and temperature. We employ a simple, mean-field theory for the high
density domain of the liquid and demonstrate that at infinite density the
mean-field theory is exact and that the system reduces to an `infinite density
ideal gas', where all correlations vanish and where the hypernetted chain (HNC)
closure becomes exact. By employing an Einstein model for the solid phases, we
subsequently calculate quantitatively the phase diagram of the model and find
that the system possesses two solid phases, face centered cubic and body
centered cubic, and also displays reentrant melting into a liquid at high
densities. Moreover, the system remains fluid at all densities when the
temperature exceeds 1% of the strength of the interactions.Comment: 22 pages, 10 figure
Exact Criterion for Determining Clustering vs. Reentrant Melting Behavior for Bounded Interaction Potentials
We examine in full generality the phase behavior of systems whose constituent
particles interact by means of potentials which do not diverge at the origin,
are free of attractive parts and decay fast enough to zero as the interparticle
separation r goes to infinity. By employing a mean field-density functional
theory which is shown to become exact at high temperatures and/or densities, we
establish a criterion which determines whether a given system will freeze at
all temperatures or it will display reentrant melting and an upper freezing
temperature.Comment: 5 pages, 3 figures, submitted to PRL on March 29, 2000 New version:
10 pages, 9 figures, forwarded to PRE on October 16, 200
Polyelectrolyte stars in planar confinement
We employ monomer-resolved Molecular Dynamics simulations and theoretical
considerations to analyze the conformations of multiarm polyelectrolyte stars
close to planar, uncharged walls. We identify three mechanisms that contribute
to the emergence of a repulsive star-wall force, namely: the confinement of the
counterions that are trapped in the star interior, the increase in
electrostatic energy due to confinement as well as a novel mechanism arising
from the compression of the stiff polyelectrolyte rods approaching the wall.
The latter is not present in the case of interaction between two
polyelectrolyte stars and is a direct consequence of the impenetrable character
of the planar wall.Comment: 34 pages, 8 figures. Revised version of the manuscript. To appear in
J. Chem. Phys. May, 200
Polydisperse star polymer solutions
We analyze the effect of polydispersity in the arm number on the effective
interactions, structural correlations and the phase behavior of star polymers
in a good solvent. The effective interaction potential between two star
polymers with different arm numbers is derived using scaling theory. The
resulting expression is tested against monomer-resolved molecular dynamics
simulations. We find that the theoretical pair potential is in agreement with
the simulation data in a much wider polydispersity range than other proposed
potentials. We then use this pair potential as an input in a many-body theory
to investigate polydispersity effects on the structural correlations and the
phase diagram of dense star polymer solutions. In particular we find that a
polydispersity of 10%, which is typical in experimental samples, does not
significantly alter previous findings for the phase diagram of monodisperse
solutions.Comment: 14 pages, 7 figure
Soft Interaction Between Dissolved Dendrimers: Theory and Experiment
Using small-angle neutron scattering and liquid integral equation theory, we
relate the structure factor of flexible dendrimers of 4th generation to their
average shape. The shape is measured as a radial density profile of monomers
belonging to a single dendrimer. From that, we derive an effective interaction
of Gaussian form between pairs of dendrimers and compute the structure factor
using the hypernetted chain approximation. Excellent agreement with the
corresponding experimental results is obtained, without the use of adjustable
parameters. The present analysis thus strongly supports the previous finding
that flexible dendrimers of low generation present fluctuating structures akin
to star polymers.Comment: 20 pages, 4 figures, submitted to Macromolecules on July 24, 200
Phase separation in star polymer-colloid mixtures
We examine the demixing transition in star polymer-colloid mixtures for star
arm numbers f=2,6,16,32 and different star-colloid size ratios. Theoretically,
we solve the thermodynamically self-consistent Rogers-Young integral equations
for binary mixtures using three effective pair potentials obtained from direct
molecular computer simulations. The numerical results show a spinodal
instability. The demixing binodals are approximately calculated, and found to
be consistent with experimental observations.Comment: 4 pages, 4 figures, submitted to PR
Exotic fluids and crystals of soft polymeric colloids
We discuss recent developments and present new findings in the colloidal
description of soft polymeric macromolecular aggregates. For various
macromolecular architectures, such as linear chains, star polymers, dendrimers
and polyelectrolyte stars, the effective interactions between suitably chosen
coordinates are shown to be ultrasoft, i.e., they either remain finite or
diverge very slowly at zero separation. As a consequence, the fluid phases have
unusual characteristics, including anomalous pair correlations and mean-field
like thermodynamic behaviour. The solid phases can exhibit exotic, strongly
anisotropic as well as open crystal structures. For example, the diamond and
the A15-phase are shown to be stable at sufficiently high concentrations.
Reentrant melting and clustering transitions are additional features displayed
by such systems, resulting in phase diagrams with a very rich topology. We
emphasise that many of these effects are fundamentally different from the usual
archetypal hard sphere paradigm. Instead, we propose that these fluids fall
into the class of mean-field fluids.Comment: 22 pages, uses iopart.cls and iopart10.clo; submitted to Journal of
Physics Condensed Matter, special issue in honour of professor Peter Puse
Soap Froths and Crystal Structures
We propose a physical mechanism to explain the crystal symmetries found in
macromolecular and supramolecular micellar materials. We argue that the packing
entropy of the hard micellar cores is frustrated by the entropic interaction of
their brush-like coronas. The latter interaction is treated as a surface effect
between neighboring Voronoi cells. The observed crystal structures correspond
to the Kelvin and Weaire-Phelan minimal foams. We show that these structures
are stable for reasonable areal entropy densities.Comment: 4 pages, RevTeX, 2 included eps figure
Can Polymer Coils be modeled as "Soft Colloids"?
We map dilute or semi-dilute solutions of non-intersecting polymer chains
onto a fluid of ``soft'' particles interacting via a concentration dependent
effective pair potential, by inverting the pair distribution function of the
centers of mass of the initial polymer chains. A similar inversion is used to
derive an effective wall-polymer potential; these potentials are combined to
successfully reproduce the calculated exact depletion interaction induced by
non-intersecting polymers between two walls. The mapping opens up the
possibility of large-scale simulations of polymer solutions in complex
geometries.Comment: 4 pages, 3 figures ReVTeX[epsfig,multicol,amssymb] references update
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