Proton transport in triflic acid pentahydrate studied via Ab initio path integral molecular dynamics

Robin L. Hayes, Stephen J. Paddison, Mark Tuckerman

Research output: Contribution to journalArticle

Abstract

Trifluoromethanesulfonic acid hydrates provide a well-defined system to study proton dissociation and transport in perfluorosulfonic acid membranes, typically used as the electrolyte in hydrogen fuel cells, in the limit of minimal water. The triflic acid pentahydrate crystal (CF 3SO 3H 3 · 5H 2O) is sufficiently aqueous that it contains an extended three-dimensional water network. Despite it being extended, however, longrange proton transport along the network is structurally unfavorable and would require considerable rearrangement. Nevertheless, the triflic acid pentahydrate crystal system can provide a clear picture of the preferred locations of local protonic defects in the water network, which provides insights about related structures in the disordered, low-hydration environment of perfluorosulfonic acid membranes. Ab initio molecular dynamics simulations reveal that the proton defect is most likely to transfer to the closest water that has the expected presolvation and only contains water in its first solvation shell. Unlike the tetrahydrate of triflic acid (CF 3SO 3H 3 · 4H 2O), there is no evidence of the proton preferentially transferring to a water molecule bridging two of the sulfonate groups. However, this could be an artifact of the crystal structure since the only such water molecule is separated from the proton by longO-Odistances.Hydrogen bonding criteria, using the two-dimensional potential of mean force, are extracted. Radial distribution functions, free energy profiles, radii of gyration, and the root-mean-square displacement computed from ab initio path integral molecular dynamics simulations reveal that quantum effects do significantly extend the size of the protonic defect and increase the frequency of proton transfer events by nearly 15%. The calculated IR spectra confirm that the dominant protonic defect mostly exists as an Eigen cation but contains some Zundel ion characteristics. Chain lengths and ring sizes determined from the hydrogen bond network, counted using graph theory techniques, are only moderately sensitive to quantum effects. Deliberately introducing a structural defect into the native crystal yields a protonic defect with one hydrogen bond to a sulfonate group that was found to be metastable for at least 10 ps.

Original languageEnglish (US)
Pages (from-to)6112-6124
Number of pages13
JournalJournal of Physical Chemistry A
Volume115
Issue number23
DOIs
StatePublished - Jun 16 2011

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Molecular dynamics
Protons
molecular dynamics
acids
protons
Water
Defects
defects
water
Hydrogen bonds
sulfonates
Crystals
hydrogen bonds
membranes
crystals
Membranes
hydrogen fuels
graph theory
Hydrogen fuels
Molecules

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Proton transport in triflic acid pentahydrate studied via Ab initio path integral molecular dynamics. / Hayes, Robin L.; Paddison, Stephen J.; Tuckerman, Mark.

In: Journal of Physical Chemistry A, Vol. 115, No. 23, 16.06.2011, p. 6112-6124.

Research output: Contribution to journalArticle

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abstract = "Trifluoromethanesulfonic acid hydrates provide a well-defined system to study proton dissociation and transport in perfluorosulfonic acid membranes, typically used as the electrolyte in hydrogen fuel cells, in the limit of minimal water. The triflic acid pentahydrate crystal (CF 3SO 3H 3 · 5H 2O) is sufficiently aqueous that it contains an extended three-dimensional water network. Despite it being extended, however, longrange proton transport along the network is structurally unfavorable and would require considerable rearrangement. Nevertheless, the triflic acid pentahydrate crystal system can provide a clear picture of the preferred locations of local protonic defects in the water network, which provides insights about related structures in the disordered, low-hydration environment of perfluorosulfonic acid membranes. Ab initio molecular dynamics simulations reveal that the proton defect is most likely to transfer to the closest water that has the expected presolvation and only contains water in its first solvation shell. Unlike the tetrahydrate of triflic acid (CF 3SO 3H 3 · 4H 2O), there is no evidence of the proton preferentially transferring to a water molecule bridging two of the sulfonate groups. However, this could be an artifact of the crystal structure since the only such water molecule is separated from the proton by longO-Odistances.Hydrogen bonding criteria, using the two-dimensional potential of mean force, are extracted. Radial distribution functions, free energy profiles, radii of gyration, and the root-mean-square displacement computed from ab initio path integral molecular dynamics simulations reveal that quantum effects do significantly extend the size of the protonic defect and increase the frequency of proton transfer events by nearly 15{\%}. The calculated IR spectra confirm that the dominant protonic defect mostly exists as an Eigen cation but contains some Zundel ion characteristics. Chain lengths and ring sizes determined from the hydrogen bond network, counted using graph theory techniques, are only moderately sensitive to quantum effects. Deliberately introducing a structural defect into the native crystal yields a protonic defect with one hydrogen bond to a sulfonate group that was found to be metastable for at least 10 ps.",
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