Structure of a uranyl peroxo complex in aqueous solution from first-principles molecular dynamics simulations
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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)2(κ1-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.
Buehl , M , Sieffert , N & Wipff , G 2014 , ' Structure of a uranyl peroxo complex in aqueous solution from first-principles molecular dynamics simulations ' Dalton Transactions , vol 43 , no. 29 , pp. 11129-11137 . DOI: 10.1039/c3dt52413b
© Royal Society of Chemistry 2014. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at http://dx.doi.org/10.1039/C3DT52413B
N.S. thanks the UJF and the CNRS for financial support and the CECIC (project: liqsim) for computer resources. NWChem calculations made use of the facilities of HECToR, the U.K. national high-performance computing service, which is provided by UoE HPCx Ltd at the University of Edinburgh, Cray Inc., and NAG Ltd and funded by the Office of Science and Technology through EPSRC's High End Computing Programme.
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