Ion–Radical Pair Separation in Larger Oxidized Water Clusters, (H2O)+n=6–21

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Department of Chemistry and Henry Eyring Center for Theoretical Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, United States
*R. P. Steele. Electronic mail address: [email protected]. Telephone: 801-878-4312.
Cite this: J. Phys. Chem. A 2016, 120, 36, 7225–7239
Publication Date (Web):August 17, 2016
https://doi.org/10.1021/acs.jpca.6b07465
Copyright © 2016 American Chemical Society
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Abstract

The structures, properties, and spectroscopic signatures of oxidized water clusters,(H2O)+n=6–21, are examined in this work, to provide fundamental insight into renewable energy and radiological processes. Computational quantum chemistry approaches are employed to sample cluster morphologies, yielding hundreds of low-lying isomers with low barriers to interconversion. The ion–radical pair-separation trend, however, which was observed in previous computational studies and in small-cluster spectroscopy experiments, is shown to continue in this larger cluster size regime. The source of this trend is preferential solvation of the hydronium ion by water, including effects beyond the first solvation shell. The fundamental conclusion of this work, therefore, is that the initially formed ion–radical dimer, which has served as a prototypical model of oxidized water, is a nascent species in large, oxidized water clusters and, very likely, bulk water.

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  • Comparison of isomer energies and harmonic zero-point energies for n = 10, 13, and 21; trends in relative isomer energies for H-deletion sampling for n = 6–21 (PDF)

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