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Issue 17, 2014
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Dynamics of actinyl ions in water: a molecular dynamics simulation study

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Abstract

The dynamics of actinyl ions (AnO2n+) in aqueous solutions is important not only for the design of advanced separation processes but also for understanding the fate of actinides in the environment. The hazardous nature of actinides makes it difficult to measure transport and thermodynamic properties experimentally, so predictive simulations are an attractive method for studying these systems. Here, we report the results of atomistic-level molecular dynamics simulations of actinyl ions (of U, Np, Pu, and Am) in their mono- and dication states in aqueous solution. Quantum mechanically derived force field parameters are used to compute self-diffusion coefficients of the actinyl ions, water exchange mechanisms, and residence times of water molecules in the first solvation shell of the actinyl ions. We find that monocation actinyl ions diffuse slightly faster than their dication counterparts. Our simulations suggest that there are two distinct water exchange mechanisms for mono and dications. An associative interchange pathway is observed for water exchange involving dication actinyls, while in monocation actinyls the exchange occurs via a dissociative mechanism. The residence time of water molecules in the first solvation shell depends on the water exchange mechanism. In the case of dications, a stiffer actinyl bond angle results in a longer residence time, while for monocations, a shorter water coordination distance leads to a longer residence time. The simulations predict much faster water exchange for UO22+ than what is observed experimentally with NMR, but other properties are consistent with experiments.

Graphical abstract: Dynamics of actinyl ions in water: a molecular dynamics simulation study

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Article information


Submitted
28 Oct 2013
Accepted
11 Mar 2014
First published
11 Mar 2014

Phys. Chem. Chem. Phys., 2014,16, 8060-8069
Article type
Paper
Author version available

Dynamics of actinyl ions in water: a molecular dynamics simulation study

S. P. Tiwari, N. Rai and E. J. Maginn, Phys. Chem. Chem. Phys., 2014, 16, 8060
DOI: 10.1039/C3CP54556C

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