Reduced-order molecular-dynamics model for polystyrene by equivalent- structure coarse graining

A Srivastava and S Ghosh, PHYSICAL REVIEW E, 85, 026702 (2012).

DOI: 10.1103/PhysRevE.85.026702

This paper develops a reduced-order equivalent-structure based model for polystyrene in a rigid body molecular dynamics framework. In general, a coarse-grained model for polymers is obtained by replacing a group of chemically connected atoms by an effective particle and deriving a coarse-grained interaction potential that reproduces the structure and dynamics at the desired length and time scale. In the current model, a detailed (similar to 16 atoms) polystyrene monomer referred to as basic structural element (BSE) is replaced by an equivalent model with spherical backbone particles and an ellipsoidal particle that represents the styrene sidegroup. The governing principals of this homogenization is based on the mass, centroid, angular momentum, and energy equivalence between the detailed and the proposed reduced-order model. The bonded interactions parameters are readily obtained in the optimization of the equivalent structure from the detailed representation. The nonbonded interactions are treated separately. In order to capture the stereochemistry of the polystyrene molecule, an anisotropic biaxial nonbonded interaction potential function known as RE-squared (RE2) interaction has been used between pairs of ellipsoidal and/or spherical particles in the system. The required calibration of the nonbonded parameters is carried out by matching with the experimental density and the local structure using radial distribution function. This homogenization process scales up the modeling system size significantly as the higher frequency motions like -C-H- vibrations and sidegroup movements are suppressed. The accuracy of the model is established by comparing fine-scale simulation with explicit representations.

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