New parametrization method for dissipative particle dynamics

Abstract

We introduce an improved method of parametrizing the Groot-Warren version of dissipative particle dynamics (DPD) by exploiting a correspondence between DPD and Scatchard-Hildebrand regular solution theory. The new parametrization scheme widens the realm of applicability of DPD by first removing the restriction of equal repulsive interactions between like beads, and second, by relating all conservative interactions between beads directly to cohesive energy densities. We establish the correspondence by deriving an expression for the Helmoltz free energy of mixing, obtaining a heat of mixing which is exactly the same form as that for a regular mixture (quadratic in the volume fraction) and an entropy of mixing which reduces to the ideal entropy of mixing for equal molar volumes. We equate the conservative interaction parameters in the DPD force law to the cohesive energy densities of the pure fluids, providing an alternative method of calculating the self-interaction parameters as well as a route to the cross interaction parameter. We validate the new parametrization by modeling the binary system SnI(4)SiCl(4), which displays liquid-liquid coexistence below an upper critical solution temperature around 140 degrees C. A series of DPD simulations were conducted at a set of temperatures ranging from 0 degrees C to above the experimental upper critical solution temperature using conservative parameters based on extrapolated experimental data. These simulations can be regarded as being equivalent to a quench from a high temperature to a lower one at constant volume. Our simulations recover the expected phase behavior ranging from solid-liquid coexistence to liquid-liquid coexistence and eventually leading to a homogeneous single phase system. The results yield a binodal curve in close agreement with the one predicted using regular solution theory, but, significantly, in closer agreement with actual solubility measurements.