How To Derive and Parameterize Effective Potentials in Colloid−Polymer Mixtures

Polymer chains in colloid−polymer mixtures can be coarse-grained by replacing them with single soft particles interacting via effective polymer−polymer and polymer−colloid pair potentials. Here we describe in detail how Ornstein−Zernike inversion techniques, originally developed for atomic and molecular fluids, can be generalized to complex fluids and used to derive effective potentials from computer simulations on a microscopic level. In particular, we consider polymer solutions for which we derive effective potentials between the centers of mass and also between mid-points or end-points from simulations of self-avoiding walk polymers. In addition, we derive effective potentials for polymers near a hard wall or a hard sphere. We emphasize the importance of including both structural and thermodynamic information (through sum rules) from the underlying simulations. In addition, we develop a simple numerical scheme to optimize the parametrization of the density-dependent polymer−polymer, polymer−wall, and polymer−sphere potentials for dilute and semidilute polymer densities, thus opening up the possibility of performing large-scale simulations of colloid−polymer mixtures. The methods developed here should be applicable to a much wider range effective potentials in complex fluids.