Chain end mobilities in polymer melts--a computational study.

Abstract

The Rouse model can be regarded as the standard model to describe the dynamics of a short polymer chain under melt conditions. In this contribution, we explicitly check one of the fundamental assumptions of this model, namely, that of a uniform friction coefficient for all monomers, on the basis of MD simulation data of a poly(ethylene oxide) (PEO) melt. This question immediately arises from the fact that in a real polymer melt, the terminal monomers have on average more intermolecular neighbors than the central monomers, and one would expect that exactly these details affect the precise value of the friction coefficient. The mobilities are determined by our recently developed statistical method, which provides detailed insights into the local polymer dynamics. Moreover, it yields complementary information to that obtained from the mean square displacement (MSD) or the Rouse mode analysis. It turns out that the Rouse assumption of a uniform mobility is fulfilled to a good approximation for the PEO melt. However, a more detailed analysis reveals that the underlying microscopic dynamics are highly affected by different contributions from intra- and intermolecular excluded volume interactions, which cannot be taken into account by a modified friction coefficient. Minor deviations occur only for the terminal monomers on larger time scales, which can be attributed to the presence of two different escape mechanisms from their first coordination sphere. These effects remain elusive when studying the dynamics with the MSD only.