Intermolecular momentum transfer in poly(perfluorosulfonic acid) membrane hydrated by aqueous solution of methanol: A molecular dynamics simulation study.

ABSTRACT

Intermolecular momentum transfer in methanol-water mixture solvated poly(perfluoro-sulfonic acid) membrane is studied in terms of center of mass velocity cross-correlation functions between molecular mass centers in their first coordination shells based on molecular dynamics simulations. Moreover, the center of mass velocity cross-correlation functions are also decomposed into longitudinal and transversal contributions. The fastest momentum transfer is observed between hydronium cation and water molecule due to the strong hydrogen bond interaction. The center of mass velocity cross-correlation functions reach peak value in about 36 fs, corresponding to a single collision with a neighboring molecule. For the momentum transfer between the water molecule and methanol molecule, the peaking time is 70 fs or about twice of that between hydronium cation and water molecule. Oscillation of the center of mass velocity cross-correlation functions between hydronium cation and water molecule is also observed due to the cage effect in their equilibrium positions.