Grand canonical Monte Carlo simulations of equilibrium polymers and networks

Grand canonical Monte Carlo (GCMC) simulation is a useful technique for mesoscale modeling of systems of self-assembled aggregates - i.e., structures at equilibrium with each other and with a pool of constituent monomers. A new biased GCMC algorithm has been developed to efficiently handle the growth and equilibration of polydisperse structures in phenomenological simulations. Its efficiency is demonstrated in a preliminary study of the nematic ordering transition in equilibrium polymers. The adaptability and precision of the GCMC approach is further shown in simulations of self-assembled networks, in which loop formation is demonstrated to suppress the first-order condensation transition for flexible chains, an effect not anticipated by mean-field theory. (C) 2003 American Chemical Society.