Liquid–liquid equilibria for soft-repulsive particles: Improved equation of state and methodology for representing molecules of different sizes and chemistry in dissipative particle dynamics

Three developments are presented that significantly expand the applicability of dissipative particle dynamics (DPD) simulations for symmetric and non-symmetric mixtures, where the former contain particles with equal repulsive parameter for self-interactions but a different repulsive parameter for cross-interactions, and the latter contain particles with different repulsive parameters also for the self-interactions. Monte Carlo and molecular dynamics simulations for unary phases covering a wide range of repulsive parameters and of densities for single-bead DPD particles point to deficiencies of the Groot and Warren equation of state (GW-EOS) [J. Chem. Phys. 107, 4423 (1997)]. A revised version, called rGW-EOS, is proposed here that is significantly more accurate over a wider range of parameters/densities. The second development is the generalization of the relationship between the Flory-Huggins χ parameter and the repulsive cross-interaction parameter when the two particles involved have different molecula...