Free energy and segregation dynamics of two channel-confined polymers of different length

TL;DR

This study uses Monte Carlo simulations to analyze how two polymers of different lengths segregate within a confined channel, revealing distinct regimes and scaling behaviors of free energy and dynamics.

Contribution

It introduces a regime map based on polymer length ratios and separation, and compares simulation results with theoretical predictions for confined polymer segregation.

Findings

Four separation regimes with distinct free energy scaling behaviors.

A regime map using length ratio and scaled separation to predict system state.

Segregation dynamics vary from diffusion-like to rapid out-of-equilibrium processes.

Abstract

Polymers confined to a narrow channel are subject to strong entropic forces that tend to drive the molecules apart. In this study, we use Monte Carlo computer simulations to study the segregation behavior of two flexible hard-sphere polymers under confinement in a cylindrical channel. We focus on the effects of using polymers of different lengths. We measure the variation of the conformational free energy, $F$, with the center-of-mass separation distance, $\lambda$. The simulations reveal four different separation regimes, characterized by different scaling properties of the free energy with respect to the polymer lengths and the channel diameter, $D$. We propose a regime map in which the state of the system is determined by the values of the quantities $N_2/N_1$ and $\lambda/(N_1+N_2)D^{-\beta}$, where $N_1$ and $N_2$ are the polymer lengths, and where $\beta\approx 0.64$. The observed scaling behavior of $F(\lambda)$ in each regime is in reasonable agreement with predictions using a simple theoretical model. In addition, we use MC dynamics simulations to study the segregation dynamics of initially overlapping polymers by measurement of the incremental mean first-passage time with respect to $\lambda$. For systems characterized by a wide range of $\lambda$ in which a short polymer is nested within a longer one, the segregation dynamics are close to that expected for two noninteracting 1D random walkers undergoing unbiased diffusion. When the free energy gradient is large segregation is rapid and characterized by out-of-equilibrium effects.