Mechanism of O(P-3) Formation from a Hydroxyl Radical Pair in Aqueous Solution
- The reaction mechanism for the rapid formation of a triplet oxygen atom, O(P-3), from a pair of triplet-state hydroxyl radicals in liquid water is explored utilizing extensive Car-Parrinello MD simulations and advanced visualization techniques. The local solvation structures, the evolution of atomic charges, atomic separations, spin densities, electron localization functions, and frontier molecular orbitals, as well as free energy profiles, evidence that the reaction proceeds through a hybrid (hydrogen atom transfer and electron proton transfer) and hemibond-assisted reaction mechanism. A benchmarking study utilizing high-level ab initio calculations to examine the interactions of a hydroxyl radical pair in the gas phase and the influence of a hemibonded water is also provided. The results presented here should serve as a foundation for further experimental and theoretical studies aimed at better understanding the role and potential applications of the triplet oxygen atom as a potent reactive oxygen species.
Author details: | Edelsys Codorniu-Hernandez, Kyle Wm. Hall, Adrian Daniel BoeseORCiD, Daniel Ziemianowicz, Sheelagh Carpendale, Peter G. Kusalik |
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DOI: | https://doi.org/10.1021/acs.jctc.5b00783 |
ISSN: | 1549-9618 |
ISSN: | 1549-9626 |
Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/26574263 |
Title of parent work (English): | Journal of chemical theory and computation |
Publisher: | American Chemical Society |
Place of publishing: | Washington |
Publication type: | Article |
Language: | English |
Year of first publication: | 2015 |
Publication year: | 2015 |
Release date: | 2017/03/27 |
Volume: | 11 |
Issue: | 10 |
Number of pages: | 9 |
First page: | 4740 |
Last Page: | 4748 |
Funding institution: | Natural Sciences and Engineering Research Council of Canada; Alberta Innovates-Technology Futures; Canadian Foundation for Innovation; Izaak Walton Killam Pre-Doctoral Scholarship Program; Vanier CGS Program; GRAND; SurfNet; NSERC; AITF; SMART Technologies; University of Calgary |
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
Peer review: | Referiert |