Molecular Dynamics Simulations of Concentrated and Dilute Aqueous Solutions of Poly(N-Isopropylacrylamide) Using a Modified OPLS-AA Model.

We perform molecular dynamics (MD) simulations of aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions using the OPLS-AA model and its modified version in combination with the TIP4P/2005 water model. The original OPLS-AA model underestimates the demixing temperature of concentrated solutions and the coil-globule transition temperature in dilute solutions, whereas the modified model reproduces both. It was reported that the transition from the globule state to the coil state never occurred in MD simulations with the original OPLS-AA model. This problem is avoided by using the modified model because of the fast dynamics near the coil-globule transition temperature, which is higher for the modified model than for the original model by ∼60 K. The distribution functions of two structural order parameters calculated from well equilibrated trajectories of the modified model clearly show that the coil-globule transition is not a discontinuous first-order transition, as suggested in previous MD studies, but a continuous transition as predicted from mean field theory. We also find that the effect of polymer-polymer hydrogen bonding on the dynamics of aggregated polymer chains is less significant than assumed in experimental studies.