Effect of counterions on the structure and stability of aqueous uranyl(VI) complexes. A first-principles molecular dynamics study
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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.
Buehl , M , Schreckenbach , G , Sieffert , N & Wipff , G 2009 , ' Effect of counterions on the structure and stability of aqueous uranyl(VI) complexes. A first-principles molecular dynamics study ' Inorganic Chemistry , vol 48 , no. 21 , pp. 9977-9979 . DOI: 10.1021/ic901298q
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see DOI: 10.1021/ic901298q
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