title: Molecular dynamics simulation of hydrated Nafion with a reactive force field for water.
abstract: We apply a newly parameterized central force field to highlight the problem of proton transport in fuel cell membranes and show that central force fields are potential candidates to describe chemical reactions on a classical level. After a short sketch of the parameterization of the force field, we validate the obtained force field for several properties of water. The experimental and simulated radial distribution functions are reproduced very accurately as a consequence of the applied parameterization procedure. Further properties, geometry, coordination, diffusion coefficient and density, are simulated adequately for our purposes. Afterwards we use the new force field for the molecular dynamics simulation of a swollen polyelectrolyte membrane similar to the widespread Nafion 117. We investigate the equilibrated structures, proton transfer, lifetimes of hydronium ions, the diffusion coefficients, and the conductivity in dependence of water content. In a short movie we demonstrate the ability of the obtained force field to describe the bond breaking/formation, and conclude that this force field can be considered as a kind of a reactive force field. The investigations of the lifetimes of hydronium ions give us the information about the kinetics of the proton transfer in a membrane with low water content. We found the evidence for the second order reaction. Finally, we demonstrate that the model is simple enough to handle the large systems sufficient to calculate the conductivity from molecular dynamics simulations. The detailed analysis of the conductivity reveals the importance of the collective moving of hydronium ions in membrane, which might give an interesting encouragement for further development of membranes.
authors.affiliation: CRS4, Parco Scientifico e Tecnologico, Sardegna Recerca, Edificio 1, 09010 Pula, Italy. hofmann@crs4.it
authors.forename: Detlef W M
authors.initials: DW
authors.lastname: Hofmann
authors.forename: Liudmila
authors.initials: L
authors.lastname: Kuleshova
authors.forename: Bruno
authors.initials: B
authors.lastname: D'Aguanno
mesh_terms: D003198:Computer Simulation; D004058:Diffusion; D004553:Electric Conductivity; D005465:Fluorocarbon Polymers / Q000737:chemistry*; D006859:Hydrogen; D008567:Membranes, Artificial; D008958:Models, Molecular; D009861:Onium Compounds; D010100:Oxygen; D011522:Protons; D014867:Water / Q000737:chemistry*
chemical_list: D005465:Fluorocarbon Polymers; D008567:Membranes, Artificial; D009861:Onium Compounds; D011522:Protons; D014867:Water; C040402:perfluorosulfonic acid; C027727:hydronium ion; D006859:Hydrogen; D010100:Oxygen