Mapping onto ideal chains overestimates self-entanglements in polymer melts

TL;DR

This study challenges the common assumption that polymer chains in melts can be modeled as ideal random walks by showing that such models overestimate knotting and self-entanglements, especially for flexible chains.

Contribution

The paper demonstrates that ideal random walk models significantly overpredict entanglements in polymer melts, highlighting the importance of residual self-avoidance effects.

Findings

Random walk models overestimate knot occurrence in melts.

Residual self-avoidance effects are significant for flexible chains.

Chains in melts resemble dilute chains near collapse, not ideal random walks.

Abstract

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 this numerical study. For melts of semiflexible chains, the effect is less pronounced. In addition, we find that chains in a melt are very similar in structure and topology to dilute single chains close to the collapse transition, which indicates that the latter are also not well-represented by random walks. We finally show that typical equilibration procedures are well-suited to relax the topology in melts.