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

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Buehl_2014_DT_Structure.pdf (731.4Kb)
Date
07/08/2014
Author
Buehl, Michael
Sieffert, Nicolas
Wipff, Georges
Keywords
Density-functional Theory
Polarizable continuum model
Water exchange-reaction
Nuclear-fuel corrosion
Hydrogen-peroxide
Liquid-water
Acetonitrile coordination
Ligand-exchange
Orbital methods
Free-energy
QD Chemistry
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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)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.
Citation
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 . https://doi.org/10.1039/c3dt52413b
Publication
Dalton Transactions
Status
Peer reviewed
DOI
https://doi.org/10.1039/c3dt52413b
ISSN
1477-9226
Type
Journal article
Rights
© 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
Description
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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  • University of St Andrews Research
URL
http://www.rsc.org/suppdata/dt/c3/c3dt52413b/c3dt52413b.pdf
URI
http://hdl.handle.net/10023/5942

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