en
Scientific article
English

Unravelling the Hydration Structure of ThX4 (X = Br, Cl) Water Solutions by Molecular Dynamics Simulations and X-ray Absorption Spectroscopy

Published inThe journal of physical chemistry. B, vol. 116, no. 22, p. 6465-6475
Publication date2012
Abstract

The hydration of Th(IV) in ThCl4 and ThBr4 water solutions at different salt concentrations was studied in order to understand the structure of Th(IV) in liquid water and the effect of Br– and Cl– anions on its hydration structure. Several theoretical methods were employed: density functional theory and classical molecular dynamics based on both semiempirical polarizable potentials and ab initio derived polarizable potentials. The results of the computations were combined with extended X-ray absorption fine structure (EXAFS) experimental data. The results of this study show that in pure water the Th–O distance of 2.45 Å corresponds to a first shell coordination number between 9 and 10. In the salt solutions, while Br– does not affect directly the hydration of Th(IV) also at relatively high concentrations, Cl–, on the other hand, is more structured around Th(IV), in agreement with recent high-energy X-ray scattering experiments. Counterions, even at relatively high concentrations (0.8 m), do not enter in the first solvation shell of Th(IV), but they induce an increase of water molecules in the first and second hydration shells of Th(IV).

Citation (ISO format)
SPEZIA, Riccardo et al. Unravelling the Hydration Structure of ThX4 (X = Br, Cl) Water Solutions by Molecular Dynamics Simulations and X-ray Absorption Spectroscopy. In: The journal of physical chemistry. B, 2012, vol. 116, n° 22, p. 6465–6475. doi: 10.1021/jp210350b
Main files (1)
Article (Published version)
accessLevelRestricted
Identifiers
ISSN of the journal1520-5207
655views
0downloads

Technical informations

Creation07/02/2012 2:52:00 PM
First validation07/02/2012 2:52:00 PM
Update time03/14/2023 5:38:35 PM
Status update03/14/2023 5:38:34 PM
Last indexation01/16/2024 12:04:33 AM
All rights reserved by Archive ouverte UNIGE and the University of GenevaunigeBlack