Combining particle and field-theoretic polymer models with multi-representation simulations.

Abstract

Listen

Translate article

Particle-based and field-theoretic simulations are both widely used methods to predict the properties of polymeric materials. In general, the advantages of each method are complementary. Field-theoretic simulations are preferred for polymers with high molecular weights and can provide direct access to chemical potentials and free energies, which makes them the method-of-choice for calculating phase diagrams. The trade-off is that field-theoretic simulations sacrifice the molecular details present in particle-based simulations, such as the configurations of individual molecules and their dynamics. In this work, we describe a new approach to conduct "multi-representation" simulations that efficiently map between particle-based and field-theoretic simulations. Our approach involves the construction of formally equivalent particle-based and field-based models, which are then simulated subject to the constraint that their spatial density profiles are equal. This constraint provides the ability to directly link particle-based and field-based simulations and enables calculations that can switch between one representation to the other. By switching between particle/field representations during a simulation, we demonstrate that our approach can leverage many of the advantages of each representation while avoiding their respective limitations. Although our method is illustrated in the context of complex sphere phases in linear diblock copolymers, we anticipate that it will be useful whenever free energies, rapid equilibration, molecular configurations, and dynamic information are all simultaneously desired.