Single-chain dynamics in a homogeneous melt and a lamellar microphase: A comparison between Smart Monte Carlo dynamics, slithering-snake dynamics, and slip-link dynamics

Abstract

We investigate the ability of Monte-Carlo algorithms to describe the single-chain dynamics in a dense homogeneous melt and a lamellar phase of a symmetric diblock copolymer. A minimal, coarse-grained model is employed that describes connectivity of effective segments by harmonic springs and where segments interact via soft potentials, which do not enforce noncrossability of the chain molecules. Studying the mean-square displacements, the dynamic structure factor, and the stress relaxation, we show that local, unconstraint displacements of segments via a Smart Monte Carlo algorithm give rise to Rouse dynamics for all but the first Monte Carlo steps. Using the slithering-snake algorithm, we observe a dynamics that is compatible with the predictions of the tube model of entangled melts for long times, but the dynamics inside the tube cannot be resolved. Using a slip-link model, we can describe the effect of entanglements and follow the different regimes of the single-chain dynamics over seven decades in time. Applications of this simulation scheme to spatially inhomogeneous systems are illustrated by studying the lamellar phase of a symmetric diblock copolymer. For the local, unconstraint dynamics, the single-chain motions parallel and perpendicular to the interfaces decouples; the perpendicular dynamics is slowed down but the parallel dynamics is identical to that in a homogeneous melt. Both the slithering-snake dynamics and the slip-link dynamics give rise to a coupling of parallel and perpendicular directions and a significant slowing down of the dynamics in the lamellar phase. (C) 2008 American Institute of Physics. [DOI: 10.1063/1.2997345]