0000000000352773
AUTHOR
Hendrik Meyer
Structural and conformational dynamics of supercooled polymer melts: Insights from first-principles theory and simulations
We report on quantitative comparisons between simulation results of a bead-spring model and mode-coupling theory calculations for the structural and conformational dynamics of a supercooled, unentangled polymer melt. We find semiquantitative agreement between simulation and theory, except for processes that occur on intermediate length scales between the compressibility plateau and the amorphous halo of the static structure factor. Our results suggest that the onset of slow relaxation in a glass-forming melt can be described in terms of monomer-caging supplemented by chain connectivity. Furthermore, a unified atomistic description of glassy arrest and of conformational fluctuations that (as…
Coarse Graining of Short Polythylene Chains for Studying Polymer Crystallization.
We derive coarse-grained models of polyethylene in the melt state with the aim to study polymer crystallization. This requires a low level of coarse-graining: We use a mapping of two CH2 groups onto one bead. The coarse-grained beads are connected with harmonic springs, an optimized angular potential, and an optional torsional potential. Coarse-grained potentials are derived from detailed all-atom simulations, and an optimized form of the force field is then derived which achieves a good accuracy in reproducing the static properties of the chains. We address the question over which temperature range such models can be used, and in particular if the model is capable of reproducing the phase…
Scale-free static and dynamical correlations in melts of monodisperse and Flory-distributed homopolymers: A review of recent bond-fluctuation model studies
It has been assumed until very recently that all long-range correlations are screened in three-dimensional melts of linear homopolymers on distances beyond the correlation length $\xi$ characterizing the decay of the density fluctuations. Summarizing simulation results obtained by means of a variant of the bond-fluctuation model with finite monomer excluded volume interactions and topology violating local and global Monte Carlo moves, we show that due to an interplay of the chain connectivity and the incompressibility constraint, both static and dynamical correlations arise on distances $r \gg \xi$. These correlations are scale-free and, surprisingly, do not depend explicitly on the compres…
Mapping onto ideal chains overestimates self-entanglements in polymer melts
In polymer physics it is typically assumed that excluded volume interactions are effectively screened in polymer melts. Hence, chains could be described by an effective random walk without excluded volume interactions. In this letter, we show that this mapping is problematic by analyzing the occurrence of knots, their spectrum and sizes in polymer melts, corresponding random walks and chains in dilute solution. The effective random walk severely overrates the occurrence of knots and their complexity, particularly when compared to melts of flexible chains, indicating that non-trivial effects due to remnants of self-avoidance still play a significant role for the chain lengths considered in t…
Long Range Bond-Bond Correlations in Dense Polymer Solutions
The scaling of the bond-bond correlation function $C(s)$ along linear polymer chains is investigated with respect to the curvilinear distance, $s$, along the flexible chain and the monomer density, $\rho$, via Monte Carlo and molecular dynamics simulations. % Surprisingly, the correlations in dense three dimensional solutions are found to decay with a power law $C(s) \sim s^{-\omega}$ with $\omega=3/2$ and the exponential behavior commonly assumed is clearly ruled out for long chains. % In semidilute solutions, the density dependent scaling of $C(s) \approx g^{-\omega_0} (s/g)^{-\omega}$ with $\omega_0=2-2\nu=0.824$ ($\nu=0.588$ being Flory's exponent) is set by the number of monomers $g(\r…
Can Soft Models Describe Polymer Knots?
Similar to macroscopic ropes and cables, long polymers create knots. We address the fundamental question whether and under which conditions it is possible to describe these intriguing objects with crude models that capture only mesoscale polymer properties. We focus on melts of long polymers which we describe by a model typical for mesoscopic simulations. A worm-like chain model defines the polymer architecture. To describe nonbonded interactions, we deliberately choose a generic "soft" repulsive potential that leads to strongly overlapping monomers and coarse local liquid structure. The soft model is parametrized to accurately reproduce mesoscopic structure and conformations of reference p…