TY  - JOUR
A1  - Codorniu-Hernandez, Edelsys
A1  - Hall, Kyle Wm.
A1  - Boese, Adrian Daniel
A1  - Ziemianowicz, Daniel
A1  - Carpendale, Sheelagh
A1  - Kusalik, Peter G.
T1  - Mechanism of O(P-3) Formation from a Hydroxyl Radical Pair in Aqueous Solution
JF  - Journal of chemical theory and computation
N2  - 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.
Y1  - 2015
U6  - https://doi.org/10.1021/acs.jctc.5b00783
SN  - 1549-9618
SN  - 1549-9626
VL  - 11
IS  - 10
SP  - 4740
EP  - 4748
PB  - American Chemical Society
CY  - Washington
ER  -