NDLI: Ultra-fast charge migration competes with proton transfer in the early chemistry of H<sub>2</sub>O˙<sup>+</sup>

Content Provider	Royal Society of Chemistry (RSC)
Author	Schmidhammer, Uli Lande, Aurélien de La Mostafavi, Mehran Wang, Furong
Copyright Year	2017
Abstract	Oxidation by the ultra-short lived radical cation of water, H2O˙+, can potentially take place at the interface of water and numerous heterogeneous systems involved in radiation therapy, energy and environmental industries. The oxidation processes induced by H2O˙+ can be mimicked in highly concentrated solutions where the nearest neighbors of H2O˙+ may be molecules other than water. The reactivity of H2O˙+ and D2O˙+ is probed in hydrogenated and deuterated sulfuric acid solutions of various concentrations. The oxidized solute, sulfate radical, is observed at 7 ps and remarkably higher yields are found in deuterated solutions. The isotopic effects reveal the competition between two ultrafast reactions: proton transfer toward H2O (D2O) and electron transfer from HSO4− to H2O˙+ (D2O˙+). Density functional theory simulations decipher the electron transfer mechanism: it proceeds via sub-femtosecond charge migration and is not affected by isotopic substitution. This work definitively demonstrates why direct oxidation triggered by H2O˙+ can be competitive with proton transfer.
Starting Page	2894
Ending Page	2899
Page Count	6
File Format	HTM / HTML PDF
ISSN	14639076
Volume Number	19
Issue Number	4
Journal	Physical Chemistry Chemical Physics
DOI	10.1039/c6cp07013b
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Properties of water Ion Density functional theory Radiation therapy Acid catalysis Sulfate
Content Type	Text
Resource Type	Article
Subject	Physics and Astronomy Physical and Theoretical Chemistry

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