Broadband 2D IR spectroscopy reveals dominant asymmetric H5O2+ proton hydration structures in acid solutions

Fournier, Joseph A.; Carpenter, William B.; Lewis, Nicholas H.  C.; Tokmakoff, Andrei

doi:10.1038/s41557-018-0091-y

Broadband 2D IR spectroscopy reveals dominant asymmetric H₅O₂⁺ proton hydration structures in acid solutions

Journal Article · Mon Jul 30 04:00:00 EDT 2018 · Nature Chemistry

DOI:https://doi.org/10.1038/s41557-018-0091-y· OSTI ID:1480907

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Univ. of Chicago, IL (United States). James Franck Inst., and Inst. for Biophysical, and Dept. of Chemistry; University of Chicago
Univ. of Chicago, IL (United States). James Franck Inst., and Inst. for Biophysical, and Dept. of Chemistry

Given its critical role in redox chemistry, determining the structure of the aqueous excess proton and the mechanism of proton transport in water remains an intense area of experimental and theoretical research. The ultrafast dynamics of the proton’s hydration structure has made experimental study extremely challenging. Using ultrafast broadband two-dimensional infrared spectroscopy, we show that the vibrational spectrum of the aqueous proton is fully consistent with a protonated water complex broadly defined as a Zundel like H₅O₂⁺ motif. Analysis of the inhomogeneously broadened proton stretch two-dimensional lineshape indicates an intrinsically asymmetric, low barrier O-H⁺-O potential that exhibits surprisingly persistent distributions in both its asymmetry and O-O distance. Finally, this structural characterization has direct implications for the extent of delocalization of the proton’s excess charge and possible mechanisms for proton transport in water.

View Accepted Manuscript (DOE)

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

Grant/Contract Number:: SC0014305

OSTI ID:: 1480907

Journal Information:: Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 9 Vol. 10; ISSN 1755-4330

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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