Infrared and NMR Spectroscopic Fingerprints of the Asymmetric H O Complex in Solution

Overview

Journal Chemphyschem

Specialty Chemistry

Date 2021 Feb 18

PMID 33599024

Citations 2

Authors

Eve Kozari

Mark Sigalov

Dina Pines

Benjamin P Fingerhut

Ehud Pines

Affiliations

Soon will be listed here.

Abstract

Infrared (IR) absorption in the 1000-3700 cm range and H NMR spectroscopy reveal the existence of an asymmetric protonated water trimer, H O in acetonitrile. The core H O motif persists in larger protonated water clusters in acetonitrile up to at least 8 water molecules. Quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) simulations reveal irreversible proton transport promoted by propagating the asymmetric H O structure in solution. The QM/MM calculations allow for the successful simulation of the measured IR absorption spectra of H O in the OH stretch region, which reaffirms the assignment of the H O spectra to a hybrid-complex structure: a protonated water dimer strongly hydrogen-bonded to a third water molecule with the proton exchanging between the two possible shared-proton Zundel-like centers. The H O structure lends itself to promoting irreversible proton transport in presence of even one additional water molecule. We demonstrate how continuously evolving H O structures may support proton transport within larger water solvates.

Citing Articles

From Local Covalent Bonding to Extended Electric Field Interactions in Proton Hydration.

Ekimova M, Kleine C, Ludwig J, Ochmann M, Agrenius T, Kozari E Angew Chem Int Ed Engl. 2022; 61(46):e202211066.

PMID: 36102247 PMC: 9827956. DOI: 10.1002/anie.202211066.

Infrared and NMR Spectroscopic Fingerprints of the Asymmetric H O Complex in Solution.

Kozari E, Sigalov M, Pines D, Fingerhut B, Pines E Chemphyschem. 2021; 22(8):716-725.

PMID: 33599024 PMC: 8252526. DOI: 10.1002/cphc.202001046.

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