Persistent Subdiffusive Proton Transport in Perfluorosulfonic Acid Membranes

Savage, John; Voth, Gregory A.

doi:10.1021/jz5014467

Persistent Subdiffusive Proton Transport in Perfluorosulfonic Acid Membranes

Journal Article · Tue Aug 19 04:00:00 EDT 2014 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/jz5014467· OSTI ID:1582234

Savage, John ^[1]; Voth, Gregory A. ^[2]

Department of Chemistry, James Franck Institute, and Computation Institute, University of Chicago, Chicago, Illinois 60637, United States; University of Chicago
Department of Chemistry, James Franck Institute, and Computation Institute, University of Chicago, Chicago, Illinois 60637, United States

Proton transport (PT) in solutions of small amphiphiles in water has previously been shown to be subdiffusive for long times. The present study analyzes simulations of hydrated perfluorosulfonic acid (PFSA) membranes in order to determine whether PT is also subdiffusive in these important amphiphilic systems. We show that PT is indeed subdiffusive for several hundred picoseconds for all hydration levels examined, and the subdiffusive behavior is highly dependent on water concentration. We also investigate the caging of the excess proton using a recently developed technique and show that the excess proton exhibits caging effects up to at least 1 ns in PFSA systems. In order to fully characterize the long-time behavior of PT in PFSAs, these results demonstrate that multiple nanosecond trajectories are needed, well beyond the current capabilities of ab initio molecular dynamics.

Research Organization:: Univ. of Chicago, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

DOE Contract Number:: SC0005418; AC02-06CH11357

OSTI ID:: 1582234

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 17 Vol. 5; ISSN 1948-7185

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

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