A molecular dynamics simulation scenario for studying solvent-mediated interactions of polymers and application to thermoresponse of poly(N-isopropylacrylamide) in water

Abstract Studying equilibrium properties of polymers in solution by atomistic simulations is a challenging task as the available computation time is often not sufficient to ensure representative sampling of the phase space. One approach to tackle this problem is to create a simulation scenario which is simple enough to enable adequate sampling of equilibrium states while it retains the essential parts of the physics of the polymer in solution. In this work, we present and test such a scenario, which is designed for studying whether a given polymer will aggregate or dissolve in a given solvent. Two periodic polymer molecules are simulated in the explicit solvent. The distance d between the polymer chains lends itself as an order parameter so that advanced sampling techniques, such as umbrella sampling, can be applied easily. A state corresponding to dissolved polymers (large d ) and a state corresponding to aggregated polymers (small d ) can be defined. The scenario misses the intramolecular collapse of the single chain, but it retains full atomistic detail regarding the polymer-solvent and the intermolecular polymer-polymer interactions. The thermoresponsive behavior of PNIPAM in water is studied with the new scenario, and it is shown that quantitative predictions of the experimental equilibrium data can be obtained after adjusting a single state-independent parameter in the force field.