In this work, we show how increasing the charge of small cations affects the structural, thermodynamical, and dynamical properties of these ions in liquid water. We have studied the case of lanthanoid and actinoid ions, for which we have recently developed accurate polarizable force fields, and the ionic radius is in the 0.995–1.250 Å range, and explored the valency range from 0 to 4+. We found that the ion charge strongly structures the neighboring water molecules and that, in this range of charges, the hydration enthalpies exhibit a quadratic dependence with respect to the charge, in line with the Born model. The diffusion process follows two main regimes: a hydrodynamical regime for neutral or low charges, and a dielectric friction regime for high charges in which the contraction of the ionic radius along the series of elements causes a decrease of the diffusion coefficient. This latter behavior can be qualitatively described by theoretical models, such as the Zwanzig and the solvated ion models. However, these models need be modified in order to obtain agreement with the observed behavior in the full charge range. We have thus modified the solvated ion model by introducing a dependence of the bare ion radius as a function of the ionic charge. Besides agreement between theory and simulation this modification allows one to obtain an empirical unified model. Thus, by analyzing the contributions to the drag coefficient from the viscous and the dielectric terms, we are able to explain the transition from a regime in which the effect of viscosity dominates to one in which dielectric friction governs the motion of ions with radii of ca. 1 Å.
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28 October 2012
Research Article|
October 22 2012
Varying the charge of small cations in liquid water: Structural, transport, and thermodynamical properties
Fausto Martelli;
Fausto Martelli
1
Université d’Evry Val d’Essonne
, Laboratoire Analyse et Modélisation pour la Biologie et l’Environnement, CNRS, UMR 8587, Boulevard F. Mitterrand, 91025 Evry Cedex, France
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Rodolphe Vuilleumier;
Rodolphe Vuilleumier
2Ecole Normale Supérieure, Département de Chimie, Paris,
France and UPMC Université Paris 06
, UMR 8640 CNRS-ENS-UPMC, Paris, France
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Jean-Pierre Simonin;
Jean-Pierre Simonin
3Laboratoire PECSA (UMR CNRS 7195),
Université P.M. Curie
, 4 Place Jussieu 75005 Paris, France
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Riccardo Spezia
Riccardo Spezia
a)
1
Université d’Evry Val d’Essonne
, Laboratoire Analyse et Modélisation pour la Biologie et l’Environnement, CNRS, UMR 8587, Boulevard F. Mitterrand, 91025 Evry Cedex, France
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Fausto Martelli
1
Rodolphe Vuilleumier
2
Jean-Pierre Simonin
3
Riccardo Spezia
1,a)
1
Université d’Evry Val d’Essonne
, Laboratoire Analyse et Modélisation pour la Biologie et l’Environnement, CNRS, UMR 8587, Boulevard F. Mitterrand, 91025 Evry Cedex, France
2Ecole Normale Supérieure, Département de Chimie, Paris,
France and UPMC Université Paris 06
, UMR 8640 CNRS-ENS-UPMC, Paris, France
3Laboratoire PECSA (UMR CNRS 7195),
Université P.M. Curie
, 4 Place Jussieu 75005 Paris, France
a)
Author to whom correspondence should be addressed. Electronic mail: [email protected].
J. Chem. Phys. 137, 164501 (2012)
Article history
Received:
August 01 2012
Accepted:
September 26 2012
Citation
Fausto Martelli, Rodolphe Vuilleumier, Jean-Pierre Simonin, Riccardo Spezia; Varying the charge of small cations in liquid water: Structural, transport, and thermodynamical properties. J. Chem. Phys. 28 October 2012; 137 (16): 164501. https://doi.org/10.1063/1.4758452
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