A bond swap algorithm for simulating dynamically crosslinked polymers

Abstract

Materials incorporating covalent adaptive networks (CAN), e.g., vitrimers, have received significant scientific attention due to their distinctive attributes of self-healing and stimuli-responsive properties. Different from direct crosslinked systems, bivalent and multivalent systems require a bond swap algorithm that respects detailed balance, considering the multiple equilibria in the system. Here, we propose a simple and robust algorithm to handle bond swap in multivalent and multi-species CAN systems. By including a bias term in the acceptance of Monte Carlo moves, we eliminate the imbalance from the bond swap site selection and multivalency effects, ensuring the detailed balance for all species in the system.