J Chem Phys. 2015 Jan 21;142(3):034904. doi: 10.1063/1.4905574.

Structure and osmotic pressure of ionic microgel dispersions.

The Journal of chemical physics

Mary M Hedrick, Jun Kyung Chung, Alan R Denton

PMID: 25612730 DOI: 10.1063/1.4905574

Abstract

We investigate structural and thermodynamic properties of aqueous dispersions of ionic microgels--soft colloidal gel particles that exhibit unusual phase behavior. Starting from a coarse-grained model of microgel macroions as charged spheres that are permeable to microions, we perform simulations and theoretical calculations using two complementary implementations of Poisson-Boltzmann (PB) theory. Within a one-component model, based on a linear-screening approximation for effective electrostatic pair interactions, we perform molecular dynamics simulations to compute macroion-macroion radial distribution functions, static structure factors, and macroion contributions to the osmotic pressure. For the same model, using a variational approximation for the free energy, we compute both macroion and microion contributions to the osmotic pressure. Within a spherical cell model, which neglects macroion correlations, we solve the nonlinear PB equation to compute microion distributions and osmotic pressures. By comparing the one-component and cell model implementations of PB theory, we demonstrate that the linear-screening approximation is valid for moderately charged microgels. By further comparing cell model predictions with simulation data for osmotic pressure, we chart the cell model's limits in predicting osmotic pressures of salty dispersions.

Publication Types

• Journal Article