Comparison of a Microgel Simulation to Poisson-Boltzmann Theory

TL;DR

This study compares simulation and Poisson-Boltzmann theory for a charged microgel, finding good agreement and validating the theoretical model for dilute conditions, while exploring factors causing discrepancies.

Contribution

The paper demonstrates the applicability of the Poisson-Boltzmann cell model to microgels and investigates the effects of charge correlations, excluded volume, and thermal fluctuations.

Findings

Good agreement between simulation and theory for counterion confinement.

Poisson-Boltzmann model is valid for dilute microgel conditions.

Charge correlations and fluctuations influence ionic distributions.

Abstract

We have investigated a single charged microgel in aqueous solution with a combined simulational model and Poisson-Boltzmann theory. In the simulations we use a coarse-grained charged bead-spring model in a dielectric continuum, with explicit counterions and full electrostatic interactions under periodic and non-periodic boundary conditions. The Poisson-Boltzmann model is that of a single charged colloid confined to a spherical cell where the counterions are allowed to enter the uniformly charged sphere. We compare the simulational results to those of the Poisson-Boltzmann solution and find good agreement, i.e., for the number of confined counterions within the gel. We then proceed to investigate the origin of the differences between the results these two models give, and performed a variety of simulations which were designed to test for the influence of charge correlations, excluded volume interactions, and thermal fluctuations in the strands of the gel. Our results support the applicability of the Poisson-Boltzman cell model to study ionic properties of small microgels under dilute conditions.