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

doi:10.1021/ic901298q

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

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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 language	English
Pages (from-to)	9977-9979
Number of pages	3
Journal	Inorganic Chemistry
Volume	48
Issue number	21
Early online date	25 Sept 2009
DOIs	https://doi.org/10.1021/ic901298q
Publication status	Published - 2 Nov 2009

Keywords

Density-functional Theory
ion
Exchange
Water

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10.1021/ic901298q

CPMD of uranyl complexes with NH4+ counterions
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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T1 - Effect of counterions on the structure and stability of aqueous uranyl(VI) complexes. A first-principles molecular dynamics study

AU - Buehl, Michael

AU - Schreckenbach, Georg

AU - Sieffert, Nicolas

AU - Wipff, Georges

PY - 2009/11/2

Y1 - 2009/11/2

N2 - 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.

AB - 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.

KW - Density-functional Theory

KW - ion

KW - Exchange

KW - Water

U2 - 10.1021/ic901298q

DO - 10.1021/ic901298q

M3 - Article

SN - 0020-1669

VL - 48

SP - 9977

EP - 9979

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 21

ER -

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

Abstract

Keywords

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