Issue 29, 2014

Structure of a uranyl peroxo complex in aqueous solution from first-principles molecular dynamics simulations

Abstract

Static ab initio and density-functional computations, as well as Car–Parrinello molecular dynamics simulations in aqueous solution are reported for [UO2(OH)(κ2-O2)(H2O)2] and [UO2(OH)21-O2H)(H2O)]. Whereas the κ1-hydroperoxo isomer is found to be more stable than the κ2-peroxo form in the gas phase, the order of stability is reversed in explicit bulk solution. Based on free energies from thermodynamic integration (BLYP functional), the peroxo form is favoured by ca. 32 kJ mol−1 in water. This stabilisation is discussed in terms of the hydration shells about the individual ligands and dipole moments of the complexes in water, and highlights the importance of explicit solute–solvent interactions and bulk solvation for the speciation of uranyl(VI) compounds.

Graphical abstract: Structure of a uranyl peroxo complex in aqueous solution from first-principles molecular dynamics simulations

Supplementary files

Article information

Article type
Paper
Submitted
02 Sep 2013
Accepted
27 Nov 2013
First published
02 Dec 2013

Dalton Trans., 2014,43, 11129-11137

Structure of a uranyl peroxo complex in aqueous solution from first-principles molecular dynamics simulations

M. Bühl, N. Sieffert and G. Wipff, Dalton Trans., 2014, 43, 11129 DOI: 10.1039/C3DT52413B

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