González-Jiménez, M. , Liao, Z. , Williams, E. L. and Wynne, K. (2024) Lifting Hofmeisters curse: Impact of cations on diffusion, hydrogen bonding and clustering of water. Journal of the American Chemical Society, 146(1), pp. 368-376. (doi: 10.1021/jacs.3c09421) (PMID:38124370)
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Abstract
Water plays a role in the stability, reactivity, and dynamics of the solutes that it contains. The presence of ions alters this capacity by changing the dynamics and structure of water. However, our understanding of how and to what extent this occurs is still incomplete. Here, a study of the low-frequency Raman spectra of aqueous solutions of various cations by using optical Kerr-effect spectroscopy is presented. This technique allows for the measurement of the changes that ions cause in both the diffusive dynamics and the vibrations of the hydrogen-bond structure of water. It is found that when salts are added, some of the water molecules become part of the ion solvation layers, while the rest retain the same diffusional properties as those of pure water. The slowing of the dynamics of the water molecules in the solvation shell of each ion was found to depend on its charge density at infinite dilution conditions and on its position in the Hofmeister series at higher concentrations. It is also observed that all cations weaken the hydrogen-bond structure of the solution and that this weakening depends only on the size of the cation. Finally, evidence is found that ions tend to form amorphous aggregates, even at very dilute concentrations. This work provides a novel approach to water dynamics that can be used to better study the mechanisms of solute nucleation and crystallization, the structural stability of biomolecules, and the dynamic properties of complex solutions, such as water-in-salt electrolytes.
| Item Type: | Articles |
|---|---|
| Additional Information: | K.W. acknowledges funding by a grant from the European Research Council (ERC) under the EuropeanUnion’sHorizon2020researchand innovation program (grant agreement no. 832703),the Engineering and Physical Sciences Research Council(EPSRC)for support through grant EP/N508792/1and EP/K034995/1,and the LeverhulmeTrustResearchProjectGrantRPG-2018-350. |
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Liao, Dr Zhiyu and Gonzalez Jimenez, Dr Mario and Wynne, Professor Klaas |
| Authors: | González-Jiménez, M., Liao, Z., Williams, E. L., and Wynne, K. |
| College/School: | College of Science and Engineering > School of Chemistry |
| Journal Name: | Journal of the American Chemical Society |
| Publisher: | American Chemical Society |
| ISSN: | 0002-7863 |
| ISSN (Online): | 1520-5126 |
| Published Online: | 20 December 2023 |
| Copyright Holders: | Copyright: © 2023 The Author(s) |
| First Published: | First published in Journal of the American Chemical Society 146(1):368-376 |
| Publisher Policy: | Reproduced under a Creative Commons licence |
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