Cationic and Anionic Impact on the Electronic Structure of Liquid Water
Yin, Z., Inhester, L., Veedu, S. T., Quevedo, W., Pietzsch, A., Wernet, P., Groenhof, G., Foehlisch, A., Grubmüller, H., & Techert, S. (2017). Cationic and Anionic Impact on the Electronic Structure of Liquid Water. Journal of Physical Chemistry Letters, 8(16), 3759-3764. https://doi.org/10.1021/acs.jpclett.7b01392
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Journal of Physical Chemistry LettersAuthors
Date
2017Copyright
© 2017 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.
Hydration shells around ions are crucial for many fundamental biological and chemical processes. Their local physicochemical properties are quite different from those of bulk water and hard to probe experimentally. We address this problem by combining soft X-ray spectroscopy using a liquid jet and molecular dynamics (MD) simulations together with ab initio electronic structure calculations to elucidate the water–ion interaction in a MgCl2 solution at the molecular level. Our results reveal that salt ions mainly affect the electronic properties of water molecules in close vicinity and that the oxygen K-edge X-ray emission spectrum of water molecules in the first solvation shell differs significantly from that of bulk water. Ion-specific effects are identified by fingerprint features in the water X-ray emission spectra. While Mg2+ ions cause a bathochromic shift of the water lone pair orbital, the 3p orbital of the Cl– ions causes an additional peak in the water emission spectrum at around 528 eV.
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American Chemical SocietyISSN Search the Publication Forum
1948-7185Publication in research information system
https://converis.jyu.fi/converis/portal/detail/Publication/27138754
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Academy of FinlandFunding program(s)
Academy Research Fellow, AoF
Additional information about funding
This works was supported by SFB755 “Nanoscale Photonic Imaging” projects B3, B4, B10 and SFB 1073 “Atomic Scale Control of Energy Conversion” project C02 of the German Science Foundation (DFG), the Max Planck Institute for Biophysical Chemistry, Deutsches Elektronen-Synchrotron, and the Helmholtz Virtual Institute “Dynamic Pathways in Multidimensional Landscapes”. S.T. is grateful for the Funds of the Chemical Industry. G.G. acknowledges financial support from the Academy of Finland (Grant 258806).

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