Fluctuation-induced forces between rings threaded around a polymer chain under tension

TL;DR

This study investigates how external tension affects polymer chain fluctuations and the resulting fluctuation-induced forces between threaded ring molecules, using molecular dynamics simulations to analyze their dependence on various parameters.

Contribution

It provides the first detailed simulation-based analysis of fluctuation-induced forces between rings on a stretched polymer chain, linking these forces to chain tension and ring properties.

Findings

Attractive fluctuation-induced force between rings proportional to temperature

Force decays with increasing ring distance

Force depends on chain stretching and ring radius

Abstract

We characterize the fluctuation properties of a polymer chain under external tension and the fluctuation-induced forces between two ring molecules threaded around the chain. The problem is relevant in the context of fluctuation-induced forces in soft matter systems, features of liquid interfaces and to describe properties of polyrotaxanes and slide-ring materials. We perform molecular dynamics simulations of the Kremer-Grest bead-spring model for the polymer and a simple ring-molecule model, in the canonical ensemble. We study transverse fluctuations of the stretched chain, as a function of chain stretching and in the presence of ring-shaped threaded molecules. The fluctuation spectra of the chains are analyzed in equilibrium at constant temperature and the differences in presence of two ring molecules are compared. For the rings located at fixed distances, we find an attractive fluctuation-induced force between the rings, proportional to the temperature and decaying with the ring distance. We characterize this force as a function of ring distance, chain stretching, ring radius and measure the differences between the free chain spectrum and the fluctuations of the chain constrained by the rings. We also compare the dependence and range of the force found in the simulations with theoretical models coming from different fields.