Effect of counterions on the structure and stability of aqueous uranyl(VI) complexes. A first-principles molecular dynamics study

Michael Buehl, Georg Schreckenbach, Nicolas Sieffert, Georges Wipff

Research output: Contribution to journalArticlepeer-review

26 Citations (Scopus)

Abstract

The inclusion of NH4+ as counterions in Car-Parrinello molecular dynamics (CPMD) simulations of anionic uranyl(VI) complexes is proposed as a viable approach to modeling "real" aqueous solutions. For [UO2F4(H2O)](2-) in water, it is shown that the inclusion of two NH4+ ions strengthens the bond between uranyl and the water ligand by ca. 2 kcal/mol, improving the accordance with experiment. According to CPMD simulations for [UO2X5]-[NH4](3) (X = F, OH) in water, the fifth fluoride is bound much stronger than the fifth OH-. Implications for a recently proposed model for oxygen exchange in uranyl hydroxide are discussed.

Original languageEnglish
Pages (from-to)9977-9979
Number of pages3
JournalInorganic Chemistry
Volume48
Issue number21
Early online date25 Sept 2009
DOIs
Publication statusPublished - 2 Nov 2009

Keywords

  • Density-functional Theory
  • ion
  • Exchange
  • Water

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