Short-Range Cooperative Slow-down of Water Solvation Dynamics Around SO42--Mg2+ Ion Pairs

dc.bibliographicCitation.firstPage506
dc.bibliographicCitation.issue6
dc.bibliographicCitation.lastPage514
dc.bibliographicCitation.volume2
dc.contributor.authorKundu, Achintya
dc.contributor.authorMamatkulov, Shavkat I.
dc.contributor.authorBrünig, Florian N.
dc.contributor.authorBonthuis, Douwe Jan
dc.contributor.authorNetz, Roland R.
dc.contributor.authorElsaesser, Thomas
dc.contributor.authorFingerhut, Benjamin P.
dc.date.accessioned2023-04-04T08:15:20Z
dc.date.available2023-04-04T08:15:20Z
dc.date.issued2022
dc.description.abstractThe presence of ions affects the structure and dynamics of water on a multitude of length and time scales. In this context, pairs of Mg2+ and SO42- ions in water constitute a prototypical system for which conflicting pictures of hydration geometries and dynamics have been reported. Key issues are the molecular pair and solvation shell geometries, the spatial range of electric interactions, and their impact on solvation dynamics. Here, we introduce asymmetric SO42- stretching vibrations as new and most specific local probes of solvation dynamics that allow to access ion hydration dynamics at the dilute concentration (0.2 M) of a native electrolyte environment. Highly sensitive heterodyne 2D-IR spectroscopy in the fingerprint region of the SO42- ions around 1100 cm-1 reveals a specific slow-down of solvation dynamics for hydrated MgSO4 and for Na2SO4 in the presence of Mg2+ ions, which manifests as a retardation of spectral diffusion compared to aqueous Na2SO4 solutions in the absence of Mg2+ ions. Extensive molecular dynamics and density functional theory QM/MM simulations provide a microscopic view of the observed ultrafast dephasing and hydration dynamics. They suggest a molecular picture where the slow-down of hydration dynamics arises from the structural peculiarities of solvent-shared SO42--Mg2+ ion pairs.eng
dc.description.versionpublishedVersioneng
dc.identifier.urihttps://oa.tib.eu/renate/handle/123456789/11884
dc.identifier.urihttp://dx.doi.org/10.34657/10917
dc.language.isoeng
dc.publisherWashington, DC : American Chemical Society
dc.relation.doihttps://doi.org/10.1021/acsphyschemau.2c00034
dc.relation.essn2694-2445
dc.relation.ispartofseriesACS Physical Chemistry Au 2 (2022), Nr. 6eng
dc.relation.issn2694-2445
dc.rights.licenseCC BY-NC-ND 4.0 Unported
dc.rights.urihttps://creativecommons.org/licenses/by-nc-nd/4.0
dc.subject2D-IR spectroscopyeng
dc.subjectcooperativityeng
dc.subjecthydration dynamicseng
dc.subjectmolecular dynamicseng
dc.subjectQM/MM simulationseng
dc.subjectsulfate ionseng
dc.subject.ddc540
dc.subject.ddc530
dc.titleShort-Range Cooperative Slow-down of Water Solvation Dynamics Around SO42--Mg2+ Ion Pairseng
dc.typearticle
dc.typeText
dcterms.bibliographicCitation.journalTitleACS Physical Chemistry Au
tib.accessRightsopenAccess
wgl.contributorMBI
wgl.subjectChemieger
wgl.subjectPhysikger
wgl.typeZeitschriftenartikelger
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