Effective Electrostatic Interactions in Solutions of Polyelectrolyte Stars with Rigid Rodlike Arms

TL;DR

This study investigates how electrostatic interactions induce anisotropy in star-branched polyelectrolytes with rigid arms, affecting their effective interactions, with findings supported by simulations and density-functional theory.

Contribution

It introduces a model combining Monte Carlo simulations and density-functional theory to analyze arm anisotropy and effective interactions in star polyelectrolytes with rigid arms.

Findings

Anisotropy increases with electrostatic strength and proximity.

Effective interactions approximate a Yukawa potential for non-overlapping stars.

Overlapping stars show close agreement between simple models and detailed simulations.

Abstract

In solutions of star-branched polyelectrolytes, electrostatic interactions between charged arms on neighboring stars can compete with intra-star interactions and rotational entropy to induce anisotropy in the orientational distribution of arms. For model stars comprising rigid rodlike arms with evenly spaced charged monomers interacting via an effective screened-Coulomb (Yukawa) potential, we explore the influence of arm orientational anisotropy on effective star-star interactions. Monte Carlo simulation and density-functional theory are used to compute arm orientational distributions and effective pair potentials between weakly charged stars. The degree of anisotropy is found to increase with the strength of electrostatic interactions and proximity of the stars. As two stars begin to overlap, the forward arms are pushed back by inter-star arm-arm repulsion, but partially interdigitate due to rotational entropy. At center-center separations approaching complete overlap, the arms relax to an isotropic distribution. For nonoverlapping stars, anisotropy-induced changes in intra- and inter-star arm-arm interactions largely cancel and the effective pair interactions are then well approximated by a simple Yukawa potential, as predicted by linear response theory for a continuum model of isotropic stars [A. R. Denton, Phys. Rev. E 67, 11804 (2003)]. For overlapping stars, the effective pair interactions in the simple rigid-arm-Yukawa model agree closely with simulations of a molecular model that includes flexible arms and explicit counterions [A. Jusufi, C. N. Likos, and H. Lowen, Phys. Rev. Lett. 88, 018301 (2002); J. Chem. Phys. 116, 11011 (2002)].