UZH-Logo

Maintenance Infos

Hydration dynamics of aqueous nitrate


Thøgersen, Jan; Réhault, Julien; Odelius, Michael; Ogden, Tom; Jena, Naresh K; Jensen, Svend J Knak; Keiding, Søren R; Helbing, Jan (2013). Hydration dynamics of aqueous nitrate. Journal of Physical Chemistry B, 117(12):3376-3388.

Abstract

Aqueous nitrate, NO3–(aq), was studied by 2D-IR, UV–IR, and UV–UV time-resolved spectroscopies in combination with molecular dynamics (MD) simulations with the purpose of determining the hydration dynamics around the anion. In water, the D3h symmetry of NO3– is broken, and the degeneracy of the asymmetric-stretch modes is lifted. This provides a very sensitive probe of the ion–water interactions. The 2D-IR measurements reveal excitation exchange between the two nondegenerate asymmetric-stretch vibrations on a 300-fs time scale concomitant with fast anisotropy decay of the diagonal-peak signals. The MD simulations show that this is caused by jumps of the transition dipole orientations related to fluctuations of the hydrogen bonds connecting the nitrate ion to the nearest water molecules. Reorientation of the ion, which is associated with the hydrogen-bond breaking, was monitored by time-resolved UV–IR and UV–UV spectroscopy, revealing a 2-ps time constant. These time scales are very similar to those reported for isotope-labeled water, suggesting that NO3–(aq) has a labile hydration shell.

Aqueous nitrate, NO3–(aq), was studied by 2D-IR, UV–IR, and UV–UV time-resolved spectroscopies in combination with molecular dynamics (MD) simulations with the purpose of determining the hydration dynamics around the anion. In water, the D3h symmetry of NO3– is broken, and the degeneracy of the asymmetric-stretch modes is lifted. This provides a very sensitive probe of the ion–water interactions. The 2D-IR measurements reveal excitation exchange between the two nondegenerate asymmetric-stretch vibrations on a 300-fs time scale concomitant with fast anisotropy decay of the diagonal-peak signals. The MD simulations show that this is caused by jumps of the transition dipole orientations related to fluctuations of the hydrogen bonds connecting the nitrate ion to the nearest water molecules. Reorientation of the ion, which is associated with the hydrogen-bond breaking, was monitored by time-resolved UV–IR and UV–UV spectroscopy, revealing a 2-ps time constant. These time scales are very similar to those reported for isotope-labeled water, suggesting that NO3–(aq) has a labile hydration shell.

Citations

21 citations in Web of Science®
21 citations in Scopus®
Google Scholar™

Altmetrics

Downloads

230 downloads since deposited on 06 Nov 2013
110 downloads since 12 months
Detailed statistics

Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2013
Deposited On:06 Nov 2013 08:27
Last Modified:05 Apr 2016 17:06
Publisher:American Chemical Society
ISSN:1520-5207
Additional Information:This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry B, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jp310090u.
Publisher DOI:https://doi.org/10.1021/jp310090u
PubMed ID:23461818
Permanent URL: https://doi.org/10.5167/uzh-84257

Download

[img]
Preview
Content: Accepted Version
Filetype: PDF
Size: 860kB
View at publisher

TrendTerms

TrendTerms displays relevant terms of the abstract of this publication and related documents on a map. The terms and their relations were extracted from ZORA using word statistics. Their timelines are taken from ZORA as well. The bubble size of a term is proportional to the number of documents where the term occurs. Red, orange, yellow and green colors are used for terms that occur in the current document; red indicates high interlinkedness of a term with other terms, orange, yellow and green decreasing interlinkedness. Blue is used for terms that have a relation with the terms in this document, but occur in other documents.
You can navigate and zoom the map. Mouse-hovering a term displays its timeline, clicking it yields the associated documents.

Author Collaborations