Shimizu, Seishi orcid.org/0000-0002-7853-1683 and Matubayasi, Nobuyuki (2018) Ion hydration::Linking self-diffusion and reorientational motion to water structure. Physical Chemistry Chemical Physics. pp. 5909-5917. ISSN 1463-9084
Abstract
Ions affect water’s self-diffusion and relaxation. Such ion-induced changes of water dynamics have long been rationalized in terms of the change of water structure around the ions. The aim of this paper is to establish a link between dynamics and the “water structure” on the basis of the extended jump (EJ) model for the reorientational motion of water, Eyring’s transition state theory of the self-diffusion of water, and the statistical thermodynamic preferential solvation theory developed from the Kirkwood-Buff (KB) theory. Through the synthesis of the above three, we formulate a scheme to correlate the ion-induced water dynamics changes to the water structure. With this new formulation, it is shown that chaotropic or negatively hydrated ions preferentially bind the transition state of water motion thereby stabilizing the transition state, whereas the exclusion of kosmotropes or positively hydrated ions suppresses the formation of the transition state. The ion effects on water dynamics are thus analyzed in a unified manner in terms of KB integrals, which represent the (averaged) “structures” of water.
Metadata
Item Type: | Article |
---|---|
Authors/Creators: |
|
Copyright, Publisher and Additional Information: | © the Owner Societies 2018. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details. |
Dates: |
|
Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Depositing User: | Pure (York) |
Date Deposited: | 19 Jan 2018 12:10 |
Last Modified: | 24 Oct 2024 00:00 |
Published Version: | https://doi.org/10.1039/c7cp07309g |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1039/c7cp07309g |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:126415 |