Mesoscale model parameters from molecular cluster calculations

摘要

We present an efficient, systematic, and universal method to estimate the interaction parameters used in mesoscale simulation methods such as dissipative particle dynamics and self-consistent field methods from molecular cluster calculations. The method is based on a generalized Flory-Huggins model in which molecules, or fragments thereof, are in contact with their van der Waals surface. We sample the density of states of molecular clusters in the space spanned by the coarse-grained degrees of freedom. From here, we calculate the sum over states and free energy of the cluster at a temperature of interest by histogram reweighting. The method allows to calculate the energy and entropy contributions to the cluster free energy explicitly. For two components, we then obtain the excess free energy of mixing and the Flory-Huggins chi-parameter, and their energetic and entropic contributions. We present two applications of the method: a simple liquid mixture of hexane and nitrobenzene, and a series of polymer blends. In the case of hexaneitrobenzene, we compare to alternative simulation methods; here we find that the energy of mixing alone is too high to explain the critical point. By including the excess entropy of mixing, however, the predicted phase behavior is in reasonable agreement with experiment. The tendency of calculations based on average energy alone to overestimate the chi-parameter is also apparent in the polymer blend calculations. (c) 2008 American Institute of Physics.