Density functional study of aqueous uranyl(VI) fluoride complexes

Michael Buehl, Nicolas Sieffert, Georges Wipff

Research output: Contribution to journalArticlepeer-review

27 Citations (Scopus)

Abstract

Mixed uranyl aquo fluoro complexes [UO2(H2O)(x)F-y](2) (y = 1-4; x + y = 4, 5) have been optimized with BLYP and B3LYP density functionals in vacuo and in a polarizable continuum modeling bulk water, and have been studied at the BLYP level with Car-Parrinello molecular dynamics ( MD) simulations. Using constrained MD simulations and thermodynamic integration, the computed free binding energy between aqueous uranyl and fluoride, affording [UO2(H2O)(4)F](+), is in excellent agreement with experiment. With the same technique, five-coordinate [UO2F4(H2O)](2) is indicated to be unstable against loss of the water ligand, as the free energy for dissociation is computed to be ca. -7 kcal/mol in aqueous solution. Crown Copyright (c) 2008 Published by Elsevier B. V. All rights reserved.

Original languageEnglish
Pages (from-to)287-293
Number of pages7
JournalChemical Physics Letters
Volume467
Issue number4-6
DOIs
Publication statusPublished - 5 Jan 2009

Keywords

  • MOLECULAR-ORBITAL METHODS
  • WATER EXCHANGE-REACTION
  • FREE-ENERGY
  • BASIS SET
  • DYNAMICS
  • ION
  • PSEUDOPOTENTIALS
  • MECHANISM
  • SOLVATION
  • MODEL

Fingerprint

Dive into the research topics of 'Density functional study of aqueous uranyl(VI) fluoride complexes'. Together they form a unique fingerprint.

Cite this