Vibrational Signatures of Electronic Properties in Oxidized Water: Unraveling the Anomalous Spectrum of the Water Dimer Cation

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Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, United States
Henry Eyring Center for Theoretical Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, United States
Cite this: J. Am. Chem. Soc. 2016, 138, 36, 11936–11945
Publication Date (Web):August 16, 2016
Copyright © 2016 American Chemical Society
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The water dimer cation, (H2O)2+, has long served as a prototypical reference system for water oxidation chemistry. In spite of this status, a definitive explanation for the anomalous—and dominant—features in the experimental vibrational spectrum [Gardenier, G. H.; Johnson, M. A.; McCoy, A. B. J. Phys. Chem. A, 2009, 113, 4772–4779] has not been determined, and harmonic analyses qualitatively fail to reproduce these features. In this computational study, accurate quantum chemistry methods are combined with a fully coupled, six-dimensional anharmonic model to show that the unassigned bands are the result of resonant mode interactions and strong anharmonic coupling. Such coupling is fundamentally due to the unique electronic structure of this open-shell ion and the manner in which auxiliary modes affect the natural charge-transfer properties of the shared-proton stretch. These unique vibrational signatures provide a key reference point for modern spectroscopic and mechanistic analyses of water-oxidation catalysts.

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  • Results for higher-dimensional, simplified models, as well as 4- and 5-D eigensolvers; Cartesian coordinates of reference structure for anharmonic computations (PDF)

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