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Solvation of positive ions in water: the dominant role of water–water interaction

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Christian Krekeler and Luigi Delle Site

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Local polarization effects, induced by monovalent and divalent positive ions in water, influence (and in turn are influenced by) the large-scale structural properties of the solvent. Experiments can only distinguish this process of interplay in a generic qualitative way. Instead, first-principles calculations can address the question at both the electronic and atomistic scale, accounting for electronic polarization as well as geometrical conformations. For this reason we study the extension of the scales' interconnection by means of first-principle Car–Parrinello molecular dynamics applied to systems of different size. In this way we identify the general aspects dominating the physics of the first solvation shell and their connection to the effects related to the formation of the outer shells and eventually the bulk. We show that while the influence of the ions is extended to the first shell only, the water–water interaction is instead playing a dominant role even within the first shell independently of the size or the charge of the ion.


PACS

61.25.Em Molecular liquids

71.15.Pd Molecular dynamics calculations (Car-Parrinello) and other numerical simulations

61.20.Ja Computer simulation of liquid structure

Subjects

Soft matter, liquids and polymers

Condensed matter: electrical, magnetic and optical

Dates

Issue 19 (16 May 2007)

Received 5 April 2007, in final form 12 April 2007

Published 20 April 2007



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