Atomistic simulations of hydrated nafion and temperature effects on hydronium ion mobility.

The effects of hydration level and temperature on the nanostructure of an atomistic model of a Nafion (DuPont) membrane and the vehicular transport of hydronium ions and water molecules were examined using classical molecular dynamics simulations. Through the determination and analysis of structural and dynamical parameters such as density, radial distribution functions, coordination numbers, mean square deviations, and diffusion coefficients, we identify that hydronium ions play an important role in modifying the hydration structure near the sulfonate groups. In the regime of low level of hydration, short hydrogen bonded linkages made of water molecules and sometimes hydronium ions alone give a more constrained structure among the sulfonate side chains. The diffusion coefficient for water was found to be in good accord with experimental data. The diffusion coefficient for the hydronium ions was determined to be much smaller (6-10 times) than that for water. Temperature was found to have a significant effect on the absolute value of the diffusion coefficients for both water and hydronium ions.