Mode-coupling theory for structural and conformational dynamics of polymer melts

TL;DR

This paper develops a mode-coupling theory for dense polymer melts that unifies structural and conformational dynamics, predicts an ideal glass transition, and aligns well with simulation data.

Contribution

It introduces a comprehensive microscopic theory for polymer melt dynamics that integrates cage effects and conformational degrees of freedom, extending the understanding of glass transition and Rouse dynamics.

Findings

Predicts an ideal glass transition independent of molecular weight for large polymers.

Provides microscopic justification for Rouse theory in polymer melts.

Results agree with computer simulations for Rouse-mode correlators and displacements.

Abstract

A mode-coupling theory for dense polymeric systems is developed which unifyingly incorporates the segmental cage effect relevant for structural slowing down and polymer chain conformational degrees of freedom. An ideal glass transition of polymer melts is predicted which becomes molecular-weight independent for large molecules. The theory provides a microscopic justification for the use of the Rouse theory in polymer melts, and the results for Rouse-mode correlators and mean-squared displacements are in good agreement with computer simulation results.