78 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
Enhanced structural correlations accelerate diffusion in charge-stabilized colloidal suspensions
Theoretical calculations for colloidal charge-stabilized and hard sphere
suspensions show that hydrodynamic interactions yield a qualitatively different
particle concentration dependence of the short-time self-diffusion coefficient.
The effect, however, is numerically small and hardly accessible by conventional
light scattering experiments. Applying multiple-scattering decorrelation
equipment and a careful data analysis we show that the theoretical prediction
for charged particles is in agreement with our experimental results from
aqueous polystyrene latex suspensions.Comment: 1 ps-file (MS-Word), 14 page
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
Short-time rotational diffusion in monodisperse charge-stabilized colloidal suspensions
We investigate the combined effects of electrostatic interactions and
hydrodynamic interactions on the short-time rotational self-diffusion
coefficient in charge-stabilized suspensions. We calculate this coefficient as
a function of volume fraction for various effective particle charges and
amounts of added electrolyte. The influence of the hydrodynamic interactions on
the rotational diffusion coefficient is less pronounced for charged particles
than for uncharged ones. Salt-free suspensions are weakly influenced by
hydrodynamic interactions. For these strongly correlated systems we obtain a
quadratic volume fraction-dependence of the diffusion coefficient, which is
well explained in terms of an effective hard sphere model.Comment: 21 pages, LaTeX, 7 Postscript figures included using epsf, to appear
in Physica
Self-diffusion coefficients of charged particles: Prediction of Nonlinear volume fraction dependence
We report on calculations of the translational and rotational short-time
self-diffusion coefficients and for suspensions of
charge-stabilized colloidal spheres. These diffusion coefficients are affected
by electrostatic forces and many-body hydrodynamic interactions (HI). Our
computations account for both two-body and three-body HI. For strongly charged
particles, we predict interesting nonlinear scaling relations and depending on volume fraction
, with essentially charge-independent parameters and . These
scaling relations are strikingly different from the corresponding results for
hard spheres. Our numerical results can be explained using a model of effective
hard spheres. Moreover, we perceptibly improve the known result for of
hard sphere suspensions.Comment: 8 pages, LaTeX, 3 Postscript figures included using eps
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
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
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
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