title: Hydration dynamics of aqueous nitrate.
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.
authors: Department of Chemistry, Aarhus University, Langelandsgade 140, DK-8000 Aarhus, Denmark. thogersen@chem.au.dk
authors: Jan
authors: J
authors: Thøgersen
authors: Julien
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authors: Réhault
authors: Michael
authors: M
authors: Odelius
authors: Tom
authors: T
authors: Ogden
authors: Naresh K
authors: NK
authors: Jena
authors: Svend J Knak
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authors: Jensen
authors: Søren R
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authors: Keiding
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