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Time-resolved terahertz–Raman spectroscopy reveals that cations and anions distinctly modify intermolecular interactions of water

The solvation of ions changes the physical, chemical and thermodynamic properties of water, and the microscopic origin of this behaviour is believed to be ion-induced perturbation of water’s hydrogen-bonding network. Here we provide microscopic insights into this process by monitoring the dissipatio...

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Autores principales: Balos, Vasileios, Kaliannan, Naveen Kumar, Elgabarty, Hossam, Wolf, Martin, Kühne, Thomas D., Sajadi, Mohsen
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9417992/
https://www.ncbi.nlm.nih.gov/pubmed/35773490
http://dx.doi.org/10.1038/s41557-022-00977-2
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author Balos, Vasileios
Kaliannan, Naveen Kumar
Elgabarty, Hossam
Wolf, Martin
Kühne, Thomas D.
Sajadi, Mohsen
author_facet Balos, Vasileios
Kaliannan, Naveen Kumar
Elgabarty, Hossam
Wolf, Martin
Kühne, Thomas D.
Sajadi, Mohsen
author_sort Balos, Vasileios
collection PubMed
description The solvation of ions changes the physical, chemical and thermodynamic properties of water, and the microscopic origin of this behaviour is believed to be ion-induced perturbation of water’s hydrogen-bonding network. Here we provide microscopic insights into this process by monitoring the dissipation of energy in salt solutions using time-resolved terahertz–Raman spectroscopy. We resonantly drive the low-frequency rotational dynamics of water molecules using intense terahertz pulses and probe the Raman response of their intermolecular translational motions. We find that the intermolecular rotational-to-translational energy transfer is enhanced by highly charged cations and is drastically reduced by highly charged anions, scaling with the ion surface charge density and ion concentration. Our molecular dynamics simulations reveal that the water–water hydrogen-bond strength between the first and second solvation shells of cations increases, while it decreases around anions. The opposite effects of cations and anions on the intermolecular interactions of water resemble the effects of ions on the stabilization and denaturation of proteins. [Image: see text]
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spelling pubmed-94179922022-08-28 Time-resolved terahertz–Raman spectroscopy reveals that cations and anions distinctly modify intermolecular interactions of water Balos, Vasileios Kaliannan, Naveen Kumar Elgabarty, Hossam Wolf, Martin Kühne, Thomas D. Sajadi, Mohsen Nat Chem Article The solvation of ions changes the physical, chemical and thermodynamic properties of water, and the microscopic origin of this behaviour is believed to be ion-induced perturbation of water’s hydrogen-bonding network. Here we provide microscopic insights into this process by monitoring the dissipation of energy in salt solutions using time-resolved terahertz–Raman spectroscopy. We resonantly drive the low-frequency rotational dynamics of water molecules using intense terahertz pulses and probe the Raman response of their intermolecular translational motions. We find that the intermolecular rotational-to-translational energy transfer is enhanced by highly charged cations and is drastically reduced by highly charged anions, scaling with the ion surface charge density and ion concentration. Our molecular dynamics simulations reveal that the water–water hydrogen-bond strength between the first and second solvation shells of cations increases, while it decreases around anions. The opposite effects of cations and anions on the intermolecular interactions of water resemble the effects of ions on the stabilization and denaturation of proteins. [Image: see text] Nature Publishing Group UK 2022-06-30 2022 /pmc/articles/PMC9417992/ /pubmed/35773490 http://dx.doi.org/10.1038/s41557-022-00977-2 Text en © The Author(s) 2022 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Balos, Vasileios
Kaliannan, Naveen Kumar
Elgabarty, Hossam
Wolf, Martin
Kühne, Thomas D.
Sajadi, Mohsen
Time-resolved terahertz–Raman spectroscopy reveals that cations and anions distinctly modify intermolecular interactions of water
title Time-resolved terahertz–Raman spectroscopy reveals that cations and anions distinctly modify intermolecular interactions of water
title_full Time-resolved terahertz–Raman spectroscopy reveals that cations and anions distinctly modify intermolecular interactions of water
title_fullStr Time-resolved terahertz–Raman spectroscopy reveals that cations and anions distinctly modify intermolecular interactions of water
title_full_unstemmed Time-resolved terahertz–Raman spectroscopy reveals that cations and anions distinctly modify intermolecular interactions of water
title_short Time-resolved terahertz–Raman spectroscopy reveals that cations and anions distinctly modify intermolecular interactions of water
title_sort time-resolved terahertz–raman spectroscopy reveals that cations and anions distinctly modify intermolecular interactions of water
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9417992/
https://www.ncbi.nlm.nih.gov/pubmed/35773490
http://dx.doi.org/10.1038/s41557-022-00977-2
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