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 - Funding Information:
We cordially acknowledge support by Stephan Figul (Advanced Microfluidic Systems GmbH) in the implementation and temperature calibration of the acetonitrile flatjet system. Funding: M. Ekimova, C. Kleine, J. Ludwig and E.T.J. Nibbering acknowledge support from the German Science Foundation (Project Nr. DFG—NI 492/11-1) and the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (ERC Grant Agreement N° 788704; E.T.J.N.). M. Odelius acknowledges support from the Carl Tryggers Foundation (contract CTS18 : 285) and the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 860553. The calculations were enabled by resources provided by the Swedish National Infrastructure for Computing (SNIC) partially funded by the Swedish Research Council through grant agreement no. 2018–05973. N. Huse gratefully acknowledges funding by the Cluster of Excellence ′CUI: Advanced Imaging of Matter′ of the Deutsche Forschungsgemeinschaft – EXC2056 – projectID390715994. E. Pines acknowledges support from the Israel Science Foundation (grant number 1587/16). We all greatly acknowledge the support of the BESSYII staff during x-ray measurements at the UE52_SGM Undulator SGM variable polarisation beamline of the Helmholtz-Zentrum Berlin and we thank Helmholtz-Zentrum Berlin for the allocation of synchrotron radiation beamtime. Authors contributions: M.E. and E.T.J.N. started and planned the project, with early add-ons by Ph.W. and M.Od.; M.E., C.K., J.L. and M.Oc. performed the XAS experiments; M.E. and C.K. analysed the XAS experimental data; E.K., D.P and E.P. performed and analysed the FT-IR experiments; T.E.G.A. and M.Od. performed and analysed the AIMD simulations; E.T.J.N. wrote the manuscript with contributions from M.E., C.K., E.P., Ph.W. and M.Od. and further amendments by J.L., M.Oc., T.E.G.A. and N.H. Open Access funding enabled and organized by Projekt DEAL.
Funding Information:
We cordially acknowledge support by Stephan Figul (Advanced Microfluidic Systems GmbH) in the implementation and temperature calibration of the acetonitrile flatjet system. Funding: M. Ekimova, C. Kleine, J. Ludwig and E.T.J. Nibbering acknowledge support from the German Science Foundation (Project Nr. DFG—NI 492/11‐1) and the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (ERC Grant Agreement N° 788704; E.T.J.N.). M. Odelius acknowledges support from the Carl Tryggers Foundation (contract CTS18 : 285) and the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska‐Curie grant agreement No 860553. The calculations were enabled by resources provided by the Swedish National Infrastructure for Computing (SNIC) partially funded by the Swedish Research Council through grant agreement no. 2018–05973. N. Huse gratefully acknowledges funding by the Cluster of Excellence ′CUI: Advanced Imaging of Matter′ of the Deutsche Forschungsgemeinschaft. E. Pines acknowledges support from the Israel Science Foundation (grant number 1587/16). We all greatly acknowledge the support of the BESSYII staff during x‐ray measurements at the UE52_SGM Undulator SGM variable polarisation beamline of the Helmholtz‐Zentrum Berlin and we thank Helmholtz‐Zentrum Berlin for the allocation of synchrotron radiation beamtime. Authors contributions: M.E. and E.T.J.N. started and planned the project, with early add‐ons by Ph.W. and M.Od.; M.E., C.K., J.L. and M.Oc. performed the XAS experiments; M.E. and C.K. analysed the XAS experimental data; E.K., D.P and E.P. performed and analysed the FT‐IR experiments; T.E.G.A. and M.Od. performed and analysed the AIMD simulations; E.T.J.N. wrote the manuscript with contributions from M.E., C.K., E.P., Ph.W. and M.Od. and further amendments by J.L., M.Oc., T.E.G.A. and N.H.. Open Access funding enabled and organized by Projekt DEAL.
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 -