TY - JOUR
T1 - From Local Covalent Bonding to Extended Electric Field Interactions in Proton Hydration
AU - Ekimova, Maria
AU - Kleine, Carlo
AU - Ludwig, Jan
AU - Ochmann, Miguel
AU - Agrenius, Thomas E.G.
AU - Kozari, Eve
AU - Pines, Dina
AU - Pines, Ehud
AU - Huse, Nils
AU - Wernet, Philippe
AU - Odelius, Michael
AU - Nibbering, Erik T.J.
N1 - Publisher Copyright:
© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
PY - 2022/11/14
Y1 - 2022/11/14
N2 - 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.
AB - 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.
KW - Eigen Cation
KW - Electronic Structure
KW - Hydrated Proton
KW - Soft X-Ray Absorption Spectroscopy
KW - Zundel Cation
UR - http://www.scopus.com/inward/record.url?scp=85140384676&partnerID=8YFLogxK
U2 - 10.1002/anie.202211066
DO - 10.1002/anie.202211066
M3 - Article
C2 - 36102247
AN - SCOPUS:85140384676
SN - 1433-7851
VL - 61
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 46
M1 - e202211066
ER -