Volume transition effects on the correlations and effective interactions among highly charged microgels

Abstract

Recent experimental studies have demonstrated the huge influence that the volume phase transition (VPT) has on the collective structure of highly charged thermo-responsive microgels in aqueous solution with low concentrations of added monovalent salt, thus opening a promising new route for controlling the overall properties of practical colloidal suspensions. We present here an analysis of this structure based on the effective electrostatic potential obtained with the exact methodology of the dressed ion theory (DIT). Starting with a description at the primitive model level, we determine the correlations among the components of our model system (macroions plus monovalent anions and cations) by utilizing the two-density integral equation theory, thus allowing us to consider realistic values for the microgel charges. The resulting microgel structure factors show a good agreement with the reported light scattering measurements, whereas the microscopic pair distributions reveal that in this regime the shrunken states promote an enhanced counterion absorption into the microgels. This packing of counterions inside the microgels induces strongly non-linear correlations among the microions, and in turn provokes a substantial weakening of the microgel–microgel correlations. The ensuing effective interactions are then obtained by contracting the description to the level in which only the macroions are present. We find not only that the magnitude and reach of the corresponding pair potentials are markedly inhibited in the shrunken states, but also that their general form diverges from the conventional screened Coulomb shape. This makes it necessary to rethink the concepts of effective charge and screening length.