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Article

Hydrogen Tunnelling as a Probe of the Involvement of Water Vibrational Dynamics in Aqueous Chemistry?

Faculty of Pharmacy and Biochemistry, University of Zagreb, A. Kovačića 1, 10 000 Zagreb, Croatia
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Molecules 2020, 25(1), 172; https://doi.org/10.3390/molecules25010172
Received: 14 November 2019 / Revised: 14 December 2019 / Accepted: 28 December 2019 / Published: 31 December 2019
(This article belongs to the Special Issue Isotope Effects 2019)
Our study of tunnelling in proton-coupled electron transfer (PCET) oxidation of ascorbate with hexacyanoferrate(III) follows the insights obtained from ultrafast 2D IR spectroscopy and theoretical studies of the vibrational water dynamics that led to the proposal of the involvement of collective intermolecular excitonic vibrational water dynamics in aqueous chemistry. To test the proposal, the hydrogen tunnelling modulation observed in the PCET reaction studied in the presence of low concentrations of various partial hydrophobic solutes in the water reaction system has been analyzed in terms of the proposed involvement of the collective intermolecular vibrational water dynamics in activation process in the case. The strongly linear correlation between common tunnelling signatures, isotopic values of Arrhenius prefactor ratios ln AH/AD and isotopic differences in activation enthalpies ΔΔH (H,D) observed in the process in fairly diluted water solutions containing various partial hydrophobic solutes (such as dioxane, acetonitrile, ethanol, and quaternary ammonium ions) points to the common physical origin of the phenomenon in all the cases. It is suggested that the phenomenon can be rooted in an interplay of delocalized collective intermolecular vibrational dynamics of water correlated with vibrations of the coupled transition configuration, where the donor-acceptor oscillations, the motions being to some degree along the reaction coordinate, lead to modulation of hydrogen tunnelling in the reaction. View Full-Text
Keywords: hydrogen tunnelling; kinetic isotope effects; water vibrational dynamics; aqueous reactivity; PCET reactions; ascorbate hydrogen tunnelling; kinetic isotope effects; water vibrational dynamics; aqueous reactivity; PCET reactions; ascorbate
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MDPI and ACS Style

Karković Marković, A.; Jakobušić Brala, C.; Pilepić, V.; Uršić, S. Hydrogen Tunnelling as a Probe of the Involvement of Water Vibrational Dynamics in Aqueous Chemistry? Molecules 2020, 25, 172. https://doi.org/10.3390/molecules25010172

AMA Style

Karković Marković A, Jakobušić Brala C, Pilepić V, Uršić S. Hydrogen Tunnelling as a Probe of the Involvement of Water Vibrational Dynamics in Aqueous Chemistry? Molecules. 2020; 25(1):172. https://doi.org/10.3390/molecules25010172

Chicago/Turabian Style

Karković Marković, Ana, Cvijeta Jakobušić Brala, Viktor Pilepić, and Stanko Uršić. 2020. "Hydrogen Tunnelling as a Probe of the Involvement of Water Vibrational Dynamics in Aqueous Chemistry?" Molecules 25, no. 1: 172. https://doi.org/10.3390/molecules25010172

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