Critical lines and phase coexistence of polymer solutions: A quantitative comparison between Wertheim's thermodynamic perturbation theory and computer simulations

Abstract

The critical behavior and phase coexistence of binary mixtures of short chain molecules and solvent, both by perturbation theory and computer simulation were investigated. It was found that simulating in the grand canonical ensemble and applying conventional histogram reweighting and finite size scaling techniques provides a reliable method for the calculation of vapor-liquid critical lines. The study of liquid-liquid immiscibility was more difficult, due to low insertion probabilities.