Interaction potential for coarse-grained models of bottlebrush polymers

Abstract

Bottlebrush polymers are a class of highly branched macromolecules that show promise for applications such as self-assembled photonic materials and tunable elastomers. However, computational studies of bottlebrush polymer solutions and melts remain challenging due to the high computational cost involved in explicitly accounting for the presence of side chains. Here, we consider a coarse-grained molecular model of bottlebrush polymers where the side chains are modeled implicitly, with the aim of expediting simulations by accessing longer length and time scales. The key ingredients of this model are the size of a coarse-grained segment and a suitably coarse-grained interaction potential between the non-bonded segments. Prior studies have not focused on developing explicit forms of such potentials, instead, relying on scaling arguments to model non-bonded interactions. Here, we show how to systematically calculate an interaction potential between the coarse-grained segments of bottlebrush from finer grained explicit side chain models using Monte Carlo and Brownian dynamics and then incorporate it into an implicit side chain model. We compare the predictions from our coarse-grained implicit side chain model with those obtained from models with explicit side chains in terms of the potential of mean force, the osmotic second virial coefficient, and the interpenetration function, highlighting the range of applicability and limitations of the coarse-grained representation. Although presented in the context of homopolymer bottlebrushes in athermal solvents, our proposed method can be extended to other solvent conditions as well as to different monomer chemistries. We expect that our implicit side chain model will prove useful for accelerating large-scale simulations of bottlebrush solutions and assembly.