87 research outputs found
Monte Carlo Simulation of Long Chain Polymer Melts: Crossover from Rouse to Reptation Dynamics
We present data of Monte Carlo simulations for monodisperse linear polymer
chains in dense melts with degrees of polymerization between N=16 and N=512.
The aim of this study is to investigate the crossover from Rouse-like dynamics
for short chains to reptation-like dynamics for long chains. To address this
problem we calculate a variety of different quantities: standard mean-square
displacements of inner monomers and of the chain's center of mass, the recently
proposed cubic invariant, persistence of bond-vector orientation with time, and
the auto-correlation functions of the bond vector, the end-to-end vector and
the Rouse modes. This analysis reveals that the crossover from non- to
entangled dynamics is very protracted. Only the largest chain length N=512,
which is about 13 times larger than the entanglement length, shows evidence for
reptation.Comment: 38 pages of REVTeX, 14 PostScript figure
On the Dynamics and Disentanglement in Thin and Two-Dimensional Polymer Films
We present results from molecular dynamics simulations of strictly
two-dimensional (2D) polymer melts and thin polymer films in a slit geometry of
thickness of the order of the radius of gyration. We find that the dynamics of
the 2D melt is qualitatively different from that of the films. The 2D monomer
mean-square displacement shows a power law at intermediate times
instead of the law expected from Rouse theory for nonentangled
chains. In films of finite thickness, chain entanglements may occur. The impact
of confinement on the entanglement length has been analyzed by a
primitive path analysis. The analysis reveals that increases
strongly with decreasing film thickness.Comment: 6 pages, 3 figures, proceedings 3rd International Workshop on
Dynamics in Confinement (CONFIT 2006
A finite excluded volume bond-fluctuation model: Static properties of dense polymer melts revisited
The classical bond-fluctuation model (BFM) is an efficient lattice Monte
Carlo algorithm for coarse-grained polymer chains where each monomer occupies
exclusively a certain number of lattice sites. In this paper we propose a
generalization of the BFM where we relax this constraint and allow the overlap
of monomers subject to a finite energy penalty \overlap. This is done to vary
systematically the dimensionless compressibility of the solution in order
to investigate the influence of density fluctuations in dense polymer melts on
various s tatic properties at constant overall monomer density. The
compressibility is obtained directly from the low-wavevector limit of the
static structure fa ctor. We consider, e.g., the intrachain bond-bond
correlation function, , of two bonds separated by monomers along the
chain. It is shown that the excluded volume interactions are never fully
screened for very long chains. If distances smaller than the thermal blob size
are probed () the chains are swollen acc ording to the classical
Fixman expansion where, e.g., . More importantly, the
polymers behave on larger distances () like swollen chains of
incompressible blobs with P(s) \si m g^0s^{-3/2}.Comment: 46 pages, 12 figure
Comparison of Dissipative Particle Dynamics and Langevin thermostats for out-of-equilibrium simulations of polymeric systems
In this work we compare and characterize the behavior of Langevin and
Dissipative Particle Dynamics (DPD) thermostats in a broad range of
non-equilibrium simulations of polymeric systems. Polymer brushes in relative
sliding motion, polymeric liquids in Poiseuille and Couette flows, and
brush-melt interfaces are used as model systems to analyze the efficiency and
limitations of different Langevin and DPD thermostat implementations. Widely
used coarse-grained bead-spring models under good and poor solvent conditions
are employed to assess the effects of the thermostats. We considered
equilibrium, transient, and steady state examples for testing the ability of
the thermostats to maintain constant temperature and to reproduce the
underlying physical phenomena in non-equilibrium situations. The common
practice of switching-off the Langevin thermostat in the flow direction is also
critically revisited. The efficiency of different weight functions for the DPD
thermostat is quantitatively analyzed as a function of the solvent quality and
the non-equilibrium situation.Comment: 12 pages, introduction improved, references added, to appear in Phys.
Rev.
Static and dynamic properties of the interface between a polymer brush and a melt of identical chains
Molecular dynamics simulations of a short-chain polymer melt between two
brush-covered surfaces under shear have been performed. The end-grafted
polymers which constitute the brush have the same chemical properties as the
free chains in the melt and provide a soft deformable substrate. Polymer chains
are described by a coarse-grained bead-spring model with Lennard-Jones
interactions between the beads and a FENE potential between nearest neighbors
along the backbone of the chains. The grafting density of the brush layer
offers a way of controlling the behavior of the surface without altering the
molecular interactions. We perform equilibrium and non-equilibrium Molecular
Dynamics simulations at constant temperature and volume using the Dissipative
Particle Dynamics thermostat. The equilibrium density profiles and the behavior
under shear are studied as well as the interdigitation of the melt into the
brush, the orientation on different length scales (bond vectors, radius of
gyration, and end-to-end vector) of free and grafted chains, and velocity
profiles. The viscosity and slippage at the interface are calculated as
functions of grafting density and shear velocity.Comment: 12 pages, submitted to J Chem Phy
Static Rouse Modes and Related Quantities: Corrections to Chain Ideality in Polymer Melts
Following the Flory ideality hypothesis intrachain and interchain excluded
volume interactions are supposed to compensate each other in dense polymer
systems. Multi-chain effects should thus be neglected and polymer conformations
may be understood from simple phantom chain models. Here we provide evidence
against this phantom chain, mean-field picture. We analyze numerically and
theoretically the static correlation function of the Rouse modes. Our numerical
results are obtained from computer simulations of two coarse-grained polymer
models for which the strength of the monomer repulsion can be varied, from full
excluded volume (`hard monomers') to no excluded volume (`phantom chains'). For
nonvanishing excluded volume we find the simulated correlation function of the
Rouse modes to deviate markedly from the predictions of phantom chain models.
This demonstrates that there are nonnegligible correlations along the chains in
a melt. These correlations can be taken into account by perturbation theory.
Our simulation results are in good agreement with these new theoretical
predictions.Comment: 9 pages, 7 figures, accepted for publication in EPJ
Nonlinear effects in charge stabilized colloidal suspensions
Molecular Dynamics simulations are used to study the effective interactions
in charged stabilized colloidal suspensions. For not too high macroion charges
and sufficiently large screening, the concept of the potential of mean force is
known to work well. In the present work, we focus on highly charged macroions
in the limit of low salt concentrations. Within this regime, nonlinear
corrections to the celebrated DLVO theory [B. Derjaguin and L. Landau, Acta
Physicochem. USSR {\bf 14}, 633 (1941); E.J.W. Verwey and J.T.G. Overbeck, {\em
Theory of the Stability of Lyotropic Colloids} (Elsevier, Amsterdam, 1948)]
have to be considered. For non--bulklike systems, such as isolated pairs or
triples of macroions, we show, that nonlinear effects can become relevant,
which cannot be described by the charge renormalization concept [S. Alexander
et al., J. Chem. Phys. {\bf 80}, 5776 (1984)]. For an isolated pair of
macroions, we find an almost perfect qualitative agreement between our
simulation data and the primitive model. However, on a quantitative level,
neither Debye-H\"uckel theory nor the charge renormalization concept can be
confirmed in detail. This seems mainly to be related to the fact, that for
small ion concentrations, microionic layers can strongly overlap, whereas,
simultaneously, excluded volume effects are less important. In the case of
isolated triples, where we compare between coaxial and triangular geometries,
we find attractive corrections to pairwise additivity in the limit of small
macroion separations and salt concentrations. These triplet interactions arise
if all three microionic layers around the macroions exhibit a significant
overlap. In contrast to the case of two isolated colloids, the charge
distribution around a macroion in a triple is found to be anisotropic.Comment: 10 pages, 9 figure
Are polymer melts "ideal"?
It is commonly accepted that in concentrated solutions or melts
high-molecular weight polymers display random-walk conformational properties
without long-range correlations between subsequent bonds. This absence of
memory means, for instance, that the bond-bond correlation function, , of
two bonds separated by monomers along the chain should exponentially decay
with . Presenting numerical results and theoretical arguments for both
monodisperse chains and self-assembled (essentially Flory size-distributed)
equilibrium polymers we demonstrate that some long-range correlations remain
due to self-interactions of the chains caused by the chain connectivity and the
incompressibility of the melt. Suggesting a profound analogy with the
well-known long-range velocity correlations in liquids we find, for instance,
to decay algebraically as . Our study suggests a precise
method for obtaining the statistical segment length \bstar in a computer
experiment.Comment: 4 pages, 3 figure
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