@article{CodorniuHernandezBoeseKusalik2013,
  author    = {Codorniu-Hernandez, Edelsys and Boese, Adrian Daniel and Kusalik, Peter G.},
  title     = {The hemibond as an alternative condensed phase structure for the hydroxyl radical},
  series = {Canadian journal of chemistry = Revue canadienne de chimie},
  volume    = {91},
  journal   = {Canadian journal of chemistry = Revue canadienne de chimie},
  number    = {7},
  publisher = {NRC Research Press},
  address   = {Ottawa},
  issn      = {0008-4042},
  doi       = {10.1139/cjc-2012-0520},
  pages     = {544 -- 551},
  year      = {2013},
  abstract  = {Despite the critical importance of the hydroxyl radical in major scientific fields, there are still open questions on the behavior of this species in the aqueous phase. In particular, there has been much debate on the existence of a hemibonded interaction between the hydroxyl radical and water molecules. While some reports indicate that the hemibonded radical might explain some experimental data, others have claimed that this interaction is simply a density functional theory (DFT) artifact. Here, we provide results from high level (basis set limit of coupled-cluster levels up to single, double, triple excitations (CCSD(T)) and beyond) ab initio calculations of different OH center dot(H2O)(n) clusters in the gas phase to accurately explore the existence of the hemibonded interaction and its energy difference with respect to other well-defined hydrogen bond interactions. Additional comparisons with second order perturbation theory (MP2) and DFT are also presented. Constrained molecular dynamics was applied to determine the free energy for the formation/disruption and ice systems. Overall, our findings confirm that the hemibond can be an alternative structure for the hydroxyl radical in the condensed phase when the formation of hydrogen bonds is impeded. These results will aid the understanding of theoretical and experimental data and help future experimental designs for the detection of this important species.},
  language  = {en}
}
@article{CodorniuHernandezHallBoeseetal.2015,
  author    = {Codorniu-Hernandez, Edelsys and Hall, Kyle Wm. and Boese, Adrian Daniel and Ziemianowicz, Daniel and Carpendale, Sheelagh and Kusalik, Peter G.},
  title     = {Mechanism of O(P-3) Formation from a Hydroxyl Radical Pair in Aqueous Solution},
  series = {Journal of chemical theory and computation},
  volume    = {11},
  journal   = {Journal of chemical theory and computation},
  number    = {10},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {1549-9618},
  doi       = {10.1021/acs.jctc.5b00783},
  pages     = {4740 -- 4748},
  year      = {2015},
  abstract  = {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.},
  language  = {en}
}