Development of a fused-sphere SAFT-gamma Mie force field for poly(vinyl alcohol) and poly(ethylene)

CC Walker and J Genzer and EE Santiso, JOURNAL OF CHEMICAL PHYSICS, 150, 034901 (2019).

DOI: 10.1063/1.5078742

SAFT-gamma Mie, a group-contribution equation of state rooted in Statistical Associating Fluid Theory, provides an efficient framework for developing accurate, transferable coarse-grained force fields for molecular simulation. Building on the success of SAFT-gamma Mie force fields for small molecules, we address two key issues in extending the SAFT-gamma Mie coarse-graining methodology to polymers: (1) the treatment of polymer chain rigidity and (2) the disparity between the structure of linear chains of tangent spheres and the structure of the real polymers. We use Boltzmann inversion to derive effective bond- stretching and angle bending potentials mapped from all-atom oligomer molecular dynamics (MD) simulations to the coarse-grained sites and a fused sphere version of SAFT-gamma Mie as the basis for non-bonded interactions. The introduction of an overlap parameter between Mie spheres leads to a degeneracy when fitting to monomer vapor-liquid equilibria (VLE) data, which we resolve by matching polymer density from coarse-grained MD simulation with that from all-atom simulation. The result is a chain of monomers rigorously parameterized to experimental VLE data and with structural detail consistent with all-atom simulations. We test our approach on atactic poly(vinyl alcohol) and polyethylene and compare the results for SAFT-gamma Mie models with structural detail mapped from the Optimized Potentials for Liquid Simulations (OPLS) and Condensed-phase Optimized Molecular Potentials for Atomistic Simulation Studies (COMPASS) all-atom force fields.

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