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DeBlase AF, Wolke CT, Weddle GH, et al. Water network-mediated, electron-induced proton transfer in [C5H5N ⋅ (H2O)n](-) clusters. J Chem Phys. 2015;143(14):144305doi: 10.1063/1.4931928.
DeBlase, A. F., Wolke, C. T., Weddle, G. H., Archer, K. A., Jordan, K. D., Kelly, J. T., Tschumper, G. S., Hammer, N. I., & Johnson, M. A. (2015). Water network-mediated, electron-induced proton transfer in [C5H5N ⋅ (H2O)n](-) clusters. The Journal of chemical physics, 143(14), 144305. https://doi.org/10.1063/1.4931928
DeBlase, Andrew F, et al. "Water network-mediated, electron-induced proton transfer in [C5H5N ⋅ (H2O)n](-) clusters." The Journal of chemical physics vol. 143,14 (2015): 144305. doi: https://doi.org/10.1063/1.4931928
DeBlase AF, Wolke CT, Weddle GH, Archer KA, Jordan KD, Kelly JT, Tschumper GS, Hammer NI, Johnson MA. Water network-mediated, electron-induced proton transfer in [C5H5N ⋅ (H2O)n](-) clusters. J Chem Phys. 2015 Oct 14;143(14):144305. doi: 10.1063/1.4931928. PMID: 26472377; PMCID: PMC4605626.
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J Chem Phys. 2015 Oct 14;143(14):144305. doi: 10.1063/1.4931928.

Water network-mediated, electron-induced proton transfer in [C5H5N ⋅ (H2O)n](-) clusters.

The Journal of chemical physics

Andrew F DeBlase, Conrad T Wolke, Gary H Weddle, Kaye A Archer, Kenneth D Jordan, John T Kelly, Gregory S Tschumper, Nathan I Hammer, Mark A Johnson

Affiliations

  1. Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520, USA.
  2. Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, Pennsylvania 15260, USA.
  3. Department of Chemistry and Biochemistry, University of Mississippi, University, Mississippi 38677, USA.

PMID: 26472377 PMCID: PMC4605626 DOI: 10.1063/1.4931928

Abstract

The role of proton-assisted charge accommodation in electron capture by a heterocyclic electron scavenger is investigated through theoretical analysis of the vibrational spectra of cold, gas phase [Py ⋅ (H2O)n=3-5](-) clusters. These radical anions are formed when an excess electron is attached to water clusters containing a single pyridine (Py) molecule in a supersonic jet ion source. Under these conditions, the cluster ion distribution starts promptly at n = 3, and the photoelectron spectra, combined with vibrational predissociation spectra of the Ar-tagged anions, establish that for n > 3, these species are best described as hydrated hydroxide ions with the neutral pyridinium radical, PyH((0)), occupying one of the primary solvation sites of the OH(-). The n = 3 cluster appears to be a special case where charge localization on Py and hydroxide is nearly isoenergetic, and the nature of this species is explored with ab initio molecular dynamics calculations of the trajectories that start from metastable arrangements of the anion based on a diffuse, essentially dipole-bound electron. These calculations indicate that the reaction proceeds via a relatively slow rearrangement of the water network to create a favorable hydration configuration around the water molecule that eventually donates a proton to the Py nitrogen atom to yield the product hydroxide ion. The correlation between the degree of excess charge localization and the evolving shape of the water network revealed by this approach thus provides a microscopic picture of the "solvent coordinate" at the heart of a prototypical proton-coupled electron transfer reaction.

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