A finite excluded volume bond-fluctuation model: Static properties of dense polymer melts revisited

TL;DR

This paper introduces a generalized bond-fluctuation model with finite monomer overlap energy, enabling systematic study of density fluctuations in dense polymer melts and revealing how excluded volume effects influence static chain properties.

Contribution

It proposes a new lattice model allowing monomer overlap with finite energy, facilitating the investigation of density fluctuation effects on static properties of dense polymer melts.

Findings

Excluded volume interactions are not fully screened for very long chains.

Chains are swollen at short distances following Fixman expansion.

At larger distances, polymers behave like swollen chains of incompressible blobs.

Abstract

The classical bond-fluctuation model (BFM) is an efficient lattice Monte Carlo algorithm for coarse-grained polymer chains where each monomer occupies exclusively a certain number of lattice sites. In this paper we propose a generalization of the BFM where we relax this constraint and allow the overlap of monomers subject to a finite energy penalty $\overlap$. This is done to vary systematically the dimensionless compressibility $g$ of the solution in order to investigate the influence of density fluctuations in dense polymer melts on various s tatic properties at constant overall monomer density. The compressibility is obtained directly from the low-wavevector limit of the static structure fa ctor. We consider, e.g., the intrachain bond-bond correlation function, $P(s)$, of two bonds separated by $s$ monomers along the chain. It is shown that the excluded volume interactions are never fully screened for very long chains. If distances smaller than the thermal blob size are probed ($s \ll g$) the chains are swollen acc ording to the classical Fixman expansion where, e.g., $P(s) \sim g^{-1}s^{-1/2}$. More importantly, the polymers behave on larger distances ($s \gg g$) like swollen chains of incompressible blobs with $P(s) \si m g^0s^{-3/2}$.