Issue 44, 2011
From the journal:

Physical Chemistry Chemical Physics

Water reorientation dynamics in the first hydration shells of F− and I−

Jean Boisson,†a   Guillaume Stirnemann,a   Damien Laage*a  and  James T. Hynes*ab  

* Corresponding authors

a Ecole Normale Supérieure, Chemistry Department, UMR CNRS-ENS-UPMC 8640, 24 rue Lhomond, 75005 Paris, France
E-mail: damien.laage@ens.fr, hynes@spot.colorado.edu

b Department of Chemistry and Biochemistry, University of Colorado, Boulder, USA

Abstract

Molecular dynamics and analytic theory results are presented for the reorientation dynamics of first hydration shell water molecules around fluoride and iodide anions. These ions represent the extremes of the (normal) halide series in terms of their size and conventional structure-making and -breaking categorizations. The simulated reorientation times are consistent with NMR and ultrafast IR experimental results. They are also in good agreement with the theoretical predictions of the analytic Extended Jump Model. Analysis through this model shows that while sudden, large amplitude jumps (in which the reorienting water exchanges hydrogen-bond partners) are the dominant reorientation pathway for the I− case, they are comparatively less important for the F− case. In particular, the diffusive reorientation of an intact F−⋯H2O hydrogen-bonded pair is found to be most important for the reorientation time, a feature related to the greater hydrogen-bond strength for the F−⋯H2O pair. The dominance of this effect for e.g. multiply charged ions is suggested.

Graphical abstract: Water reorientation dynamics in the first hydration shells of F− and I−

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Article information

DOI
https://doi.org/10.1039/C1CP21834D
Article type
Paper
Submitted
07 Jun 2011
Accepted
24 Aug 2011
First published
13 Sep 2011

Phys. Chem. Chem. Phys., 2011,13, 19895-19901

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Water reorientation dynamics in the first hydration shells of F− and I−

J. Boisson, G. Stirnemann, D. Laage and J. T. Hynes, Phys. Chem. Chem. Phys., 2011, 13, 19895 DOI: 10.1039/C1CP21834D

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