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

Seemingly simple yet surprisingly difficult to probe, excess protons in water constitute complex quantum objects with strong interactions with the extended and dynamically changing hydrogen-bonding network of the liquid. Proton hydration plays pivotal roles in energy transport in hydrogen fuel cells and signal transduction in transmembrane proteins. While geometries and stoichiometry have been widely addressed in both experiment and theory, the electronic structure of these specific hydrated proton complexes has remained elusive. Here we show, layer by layer, how utilizing novel flatjet technology for accurate x-ray spectroscopic measurements and combining infrared spectral analysis and calculations, we find orbital-specific markers that distinguish two main electronic-structure effects: Local orbital interactions determine covalent bonding between the proton and neigbouring water molecules, while orbital-energy shifts measure the strength of the extended electric field of the proton.

Infrared and NMR Spectroscopic Fingerprints of the Asymmetric H7 + O3 Complex in Solution.

The front cover artwork is provided by the groups of Prof. Ehud Pines (BGU, Israel) and Dr. Benjamin Fingerhut (MBI, Berlin). The image shows a scientist integrating experiments with theory for resolving the structural diffusion of the aqueous proton in acetonitrile providing a novel view on the Grotthuss mechanism. Read the full text of the Article at 10.1002/cphc.202001046.

Infrared and NMR Spectroscopic Fingerprints of the Asymmetric H7+ O3 Complex in Solution.

Infrared (IR) absorption in the 1000-3700 cm-1 range and 1 H NMR spectroscopy reveal the existence of an asymmetric protonated water trimer, H7+ O3, in acetonitrile. The core H7+ O3 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 H7+ O3 structure in solution. The QM/MM calculations allow for the successful simulation of the measured IR absorption spectra of H7+ O3 in the OH stretch region, which reaffirms the assignment of the H7+ O3 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 H7+ O3 structure lends itself to promoting irreversible proton transport in presence of even one additional water molecule. We demonstrate how continuously evolving H7+ O3 structures may support proton transport within larger water solvates.