Thermodynamics of Confined Knotted Lattice Polygons

TL;DR

This paper investigates how the topology of confined knotted ring polymers influences their thermodynamic phase transitions and free energy, revealing that knot type affects their behavior near critical points.

Contribution

It introduces a lattice knot model showing that the thermodynamic phase transition depends on the polymer's knot type, highlighting the topological influence on confined ring polymers.

Findings

Phase transition occurs between solvent-rich and polymer-rich phases for various knot types.

Small variations in free energy are observed near the critical point for different knots.

Thermodynamic properties depend on the topological entanglement of the polymer.

Abstract

A ring polymer in a confining space may exhibit at least two phases, namely an expanded (or solvent-rich phase) if its concentration is small, or a collapsed (or polymer-rich phase) when it is concentrated and compressed. These phases are discussed in reference \cite{deG79}, and have been modelled, traditionally, in the mean field using Flory-Huggins theory \cite{Flory42,Huggins42}. In three dimensions the ring polymer may also be knotted, or linked, and have its conformational degrees of freedom constrained by its topology. In a lattice model of confined knotted ring polymers there are indications that the thermodynamic properties of the ring polymer (for example, the osmotic pressure \cite{GJvR18,JvR19}) is a function of its topology. In this paper we explore a lattice knot model of a confined ring polymer as a function of its chemical potential. We show that a well-defined phase transition occurs between solvent-rich and polymer-rich phases when the lattice knot exhibits either the unknot topology or any other fixed knot type. Furthermore, we observe small yet significant variations in the free energy near the critical point when comparing trefoil knots with other non-trivial knot types. These findings indicate that the thermodynamic properties of confined ring polymers depend on their topological entanglement characteristics (namely, their knot type).