Equilibrium polymerization in the Stockmayer fluid as a model of supermolecular self-organization

Abstract

A diverse range of molecular self-organization processes arises from a competition between directional and isotropic van der Waals intermolecular interactions. We conduct Monte Carlo simulations of the Stockmayer fluid (SF) with a large dipolar interaction as a minimal self-organization model and focus on basic thermodynamic properties that are needed to characterize the polymerization transition that occurs in this fluid. In particular, we determine the polymerization transition lines from the maximum in the specific heat, C(v), and the inflection point in the extent of polymerization, Phi. We also characterize the geometry (radius of gyration R(g), chain length L, chain topology) of the clusters that form in this associating fluid as a function of temperature, T, and concentration, rho . The pressure, P, and the second virial coefficient, B2, were determined, since these properties contain essential information about the strength of the isotropic (van der Waals) interactions. Our simulations indicate that the locations of the polymerization lines are quantitatively consistent with a model of equilibrium polymerization with the enthalpy of polymerization ("sticking energy") fixed by the minimum in the intermolecular potential. The polymerization transition in the SF is accompanied by a topological transition from predominantly linear to ring polymers upon cooling that is driven by the minimization of the dipolar energy of the clusters. We also find that the basic interaction parameters describing polymerization and phase separation in the SF can be estimated based on the existing theory of equilibrium polymerization, but the theory must be refined to account for ring formation in order to accurately describe the configurational properties of this model self-organizing fluid.