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

Michael Buehl; Nicolas Sieffert; Georges Wipff

doi:10.1039/c3dt52413b

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

Michael Buehl^*, Nicolas Sieffert, Georges Wipff

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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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.

Original language	English
Pages (from-to)	11129-11137
Number of pages	9
Journal	Dalton Transactions
Volume	43
Issue number	29
Early online date	2 Dec 2013
DOIs	https://doi.org/10.1039/c3dt52413b
Publication status	Published - 7 Aug 2014

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

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10.1039/c3dt52413b

Buehl_2014_DT_Structure
© 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
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title = "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)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.",

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",

author = "Michael Buehl and Nicolas Sieffert and Georges Wipff",

note = "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. ",

year = "2014",

month = aug,

day = "7",

doi = "10.1039/c3dt52413b",

language = "English",

volume = "43",

pages = "11129--11137",

journal = "Dalton Transactions",

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publisher = "ROYAL SOC CHEMISTRY",

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T1 - Structure of a uranyl peroxo complex in aqueous solution from first-principles molecular dynamics simulations

AU - Buehl, Michael

AU - Sieffert, Nicolas

AU - Wipff, Georges

N1 - 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.

PY - 2014/8/7

Y1 - 2014/8/7

N2 - 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.

AB - 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.

KW - Density-functional Theory

KW - Polarizable continuum model

KW - Water exchange-reaction

KW - Nuclear-fuel corrosion

KW - Hydrogen-peroxide

KW - Liquid-water

KW - Acetonitrile coordination

KW - Ligand-exchange

KW - Orbital methods

KW - Free-energy

UR - http://www.rsc.org/suppdata/dt/c3/c3dt52413b/c3dt52413b.pdf

U2 - 10.1039/c3dt52413b

DO - 10.1039/c3dt52413b

M3 - Article

SN - 1477-9226

VL - 43

SP - 11129

EP - 11137

JO - Dalton Transactions

JF - Dalton Transactions

IS - 29

ER -

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

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