Approximate additivity in the solvent-mediated potential of mean force for ultrasoft particle systems

Abstract

In the infinite dilution limit, we show that the solvent-mediated potential of mean force (PMF) between solutes, extracted from the hypernetted-chain (HNC) closure of the Ornstein-Zernike equations, can expressed as a convolution between solute-specific generalised excluded volume functions. In the limit of a structureless solvent of point particles and hard core solutes, this recovers the exact Asakura-Oosawa depletion potential as the overlap between excluded volume spheres. The methodology can be deployed for ultrasoft particle systems such as those encountered in dissipative particle dynamics (DPD), where the solvent-mediated PMF can be recovered with considerable accuracy. These results confirm that in coarse-grained molecular DPD simulations the parametrisation of the non-bonded repulsions is sensitive to the assumed intramolecular bond lengths if they are smaller than the range of the DPD potential, due to the overlap of the soft excluded volume functions.