Dynamical heterogeneities in non-entangled polystyrene and poly(ethylene oxide) star melts

TL;DR

This study uses atomistic simulations to investigate heterogeneous dynamics in non-entangled star-shaped polymers, comparing results with Rouse models and highlighting the importance of chemical details in understanding polymer mobility.

Contribution

It provides a detailed atomistic analysis of dynamical heterogeneities in star polymers and critically evaluates Rouse model assumptions for these complex architectures.

Findings

Rouse models partially describe the dynamics but fail to capture mobility gradients.

Heterogeneous dynamics originate from the star-like architecture and vary at the Kuhn length scale.

Chemical details are crucial for accurate modeling of star polymer dynamics.

Abstract

Star polymers can exhibit a heterogeneous dynamical behavior due to their internal structure. In this work we employ atomistic molecular dynamics simulations to study translational motion in non-entangled polystyrene and poly(ethylene oxide) star-shaped melts. We focus on the local heterogeneous dynamics originating from the multi-arm star-like architecture and quantify the intramolecular dynamical gradient. By examining the translational motion at length scales of the order of the Kuhn length, we aim to find common features for both studied chemistries and to provide a critical and direct comparison with theoretical models of polymer dynamics. We discuss the observed tendencies with respect to the continuous Rouse model adjusted for the star-like architectures. Two versions of the Rouse model are examined: one assuming uniform friction on every Rouse bead and another one considering larger branch point friction. Apart from chain connectivity between neighboring beads, both versions disregard interactions between the chains. Despite the tolerable description of the simulation data, neither model appears to reflect the mobility gradient accurately. The detailed quantitative atomistic models employed here bridge the gap between the theoretical and general, coarse-granined models of star-like polymers which lack the indispensable chemical details.