PolySMart: a general coarse-grained molecular dynamics polymerization scheme

Abstract

The development of simulation methods to study the structure and dynamics of a macroscopically sized piece of polymer material is important as such methods can elucidate structure–property relationships. Several methods have been reported to construct initial structures for homo- and co-polymers; however, most of them are only useful for short linear polymers since one needs to pack and equilibrate the far-from-equilibrium initial structures, which is a tedious task for long or hyperbranched polymers and unfeasible for polymer networks. In this method article, we present PolySMart, i.e., an open-source python package, which can effectively produce fully equilibrated homo- and hetero-polymer melts and solutions with no limitation on the polymer topology and size, at a coarse-grained resolution and through a bottom-up approach. This python package is also capable of exploring the polymerization kinetics through its reactive scheme in realistic conditions so that it can model the multiple co-occurring polymerization reactions (with different reaction rates) as well as consecutive polymerizations under stoichiometric and non-stoichiometric conditions. Thus, the equilibrated polymer models are generated through correct polymerization kinetics. A benchmark and verification of the performance of the program for several realistic cases, i.e., for homo-polymers, co-polymers, and crosslinked networks, is given. We further discuss the capability of the program to contribute to the discovery and design of new polymer materials.