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The hydration structure of the heavy-alkalines Rb+ and Cs+ through Molecular Dynamics and X-ray Absorption spectroscopy: surface clusters and eccentricity

Abstract

Physicochemical properties of the two heaviest stable alkaline cations, Rb+ and Cs+ , in water have been examined from classical Molecular Dynamics (MD) simulations. Alkaline-water intermolecular potentials have been built from ab initio interaction energies of [M(H2O)n]+ clusters. Differing from other monatomic metal cations, the sampling needed the inclusion of surface clusters to properly describe the interactions. First coordination shell is found at an average M-Odistance of 2.87 Å and 3.12 Å for Rb+ and Cs+, respectively, with coordination numbers of 8 and 10. Structural, dynamical and energetic properties are discussed on the basis of the delicate compromise among the ion-water and water-water interactions which contribute almost on the same foot to the definition of the solvent structure around the ions. A significant asymmetry is detected in the Rb+ and Cs+ first hydration shell. Reorientational times of first-shell water molecules for Cs+ support a clear structure-breaking nature for this cation, whereas the Rb+ values do not allow differ from pure water behavior. Experimental EXAFS and XANES spectra have been compared to simulated ones, obtained by means of the application of the FEFF code to a set of statistically significant structures taken from the MD simulations. Due to the presence of multi-excitations in the absorption spectra, the theoretical-experimental agreement for the EXAFS spectra is reached when the multi-excitations are removed from the experimental spectra.

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Publication details

The article was received on 07 Aug 2017, accepted on 03 Oct 2017 and first published on 04 Oct 2017


Article type: Paper
DOI: 10.1039/C7CP05346K
Citation: Phys. Chem. Chem. Phys., 2017, Accepted Manuscript
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    The hydration structure of the heavy-alkalines Rb+ and Cs+ through Molecular Dynamics and X-ray Absorption spectroscopy: surface clusters and eccentricity

    D. Z. Caralampio, J. Manuel Martínez Fernandez, R. R. Rodríguez Pappalardo and E. Sanchez Marcos, Phys. Chem. Chem. Phys., 2017, Accepted Manuscript , DOI: 10.1039/C7CP05346K

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