Effect of Counterions on the Structure and Stability of Aqueous Uranyl(VI) Complexes. A First-Principles Molecular Dynamics Study

Bühl, Michæl; Schreckenbach, Georg; Sieffert, Nicolas; Wipff, Georges

doi:10.1021/ic901298q

Cited by 25 publications

(6 citation statements)

References 18 publications

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“…Theoretical studies involving actinyl ions in aqueous and other environments can be classified into two broad categories. On one hand, one can use computationally expensive quantum mechanical calculations and ab initio molecular dynamics simulations 14,16,[25][26][27] to understand the characteristics of uranyl ions in water clusters and bulk aqueous solutions. Garcia-Hernandez et al 25 and Buhl et al 26,27 have not only investigated the effect of counter-ions on the stability of uranyl(VI) complexes but also predicted the free energy profile of the dynamic solvent exchange between the bulk and the solvation shell.…”

Section: Introductionmentioning

confidence: 99%

“…On one hand, one can use computationally expensive quantum mechanical calculations and ab initio molecular dynamics simulations 14,16,[25][26][27] to understand the characteristics of uranyl ions in water clusters and bulk aqueous solutions. Garcia-Hernandez et al 25 and Buhl et al 26,27 have not only investigated the effect of counter-ions on the stability of uranyl(VI) complexes but also predicted the free energy profile of the dynamic solvent exchange between the bulk and the solvation shell. On the other hand, force-field based classical molecular dynamics simulations, which provide a computationally inexpensive but accurate enough method to understand the structure as well as the dynamics of these ions in different condensed phase environments, are extensively used now-a-days.…”

Section: Introductionmentioning

confidence: 99%

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Molecular dynamics simulation study of distribution and dynamics of aqueous solutions of uranyl ions: the effect of varying temperature and concentration

Chopra

Choudhury

2015

Phys. Chem. Chem. Phys.

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Investigating the characteristics of actinyl ions has been of great interest due to their direct relevance in the nuclear fuel cycle. All-atom molecular dynamics simulations have been employed to study the orientational structure and dynamics of aqueous solutions of uranyl ions of various concentrations. The orientational structure of water around a uranyl ion has been thoroughly investigated by calculating different orientational probability distributions corresponding to different molecular axes of water. The orientational distribution of water molecules in the first coordination shell of a uranyl ion is found to be markedly different from that in bulk water. Analysis of counterion distribution around the uranyl ion reveals the presence of nitrate ions along with water molecules in the first solvation shell. From the comparison of the number of coordinated water and nitrate ions at various uranyl nitrate concentrations, it is evident that these two species compete for occupying the first solvation shell of the uranyl ion. Orientational dynamics of water molecules about different molecular axes of water in the vicinity of uranyl ions have also been investigated and decreasing orientational mobility of water with increasing uranyl concentration has been found. However, it is observed that the orientational dynamics remains more or less the same whether we consider all the water molecules in the aqueous solution or only the solvation shell water molecules. The effect of temperature on the translational and orientational characteristics of the aqueous uranyl solutions has also been studied in detail.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Molecular dynamics simulation study of distribution and dynamics of aqueous solutions of uranyl ions: the effect of varying temperature and concentration

Chopra

Choudhury

2015

Phys. Chem. Chem. Phys.

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“…However, the orientation of such water is not at all obvious and requires input from molecular dynamics simulations. [70][71][72] Therefore exclusively spectra of positively charged species are compared in Fig. 8 (complexes 1 : 3 and 3 : 7 not shown).…”

Section: As Expected the Lifetimes Increase With Decreasingmentioning

confidence: 99%

Combining luminescence spectroscopy, parallel factor analysis and quantum chemistry to reveal metal speciation – a case study of uranyl(vi) hydrolysis

et al. 2015

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“…48 However, it is known that Np(V) will disproportionate to Np(VI) and Np(IV) under a variety of conditions. 48 The relative stabilities between these oxidation states can be significantly affected by numerous factors such as concentration, 49 temperature, 50 counter ions, 51 radiolysis, 52 and hydrolysis. 19 A significant numbers of known neptunium compounds are mixed-valent containing Np(IV)/Np(V) or Np(V)/Np(VI).…”

Section: Neptunium Boratesmentioning

confidence: 99%

Recent progress in actinide borate chemistry

et al. 2011

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The use of molten boric acid as a reactive flux for synthesizing actinide borates has been developed in the past two years providing access to a remarkable array of exotic materials with both unusual structures and unprecedented properties.[ThB 5 O 6 (OH) 6 ][BO(OH) 2 ]Á2.5H 2 O possesses a cationic supertetrahedral structure and displays remarkable anion exchange properties with high selectivity for TcO 4 À . Uranyl borates form noncentrosymmetric structures with extraordinarily rich topological relationships. Neptunium borates are often mixed-valent and yield rare examples of compounds with one metal in three different oxidation states. Plutonium borates display new coordination chemistry for trivalent actinides. Finally, americium borates show a dramatic departure from plutonium borates, and there are scant examples of families of actinides compounds that extend past plutonium to examine the bonding of later actinides. There are several grand challenges that this work addresses. The foremost of these challenges is the development of structure-property relationships in transuranium materials. A deep understanding of the materials chemistry of actinides will likely lead to the development of advanced waste forms for radionuclides present in nuclear waste that prevent their transport in the environment. This work may have also uncovered the solubility-limiting phases of actinides in some repositories, and allows for measurements on the stability of these materials.

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Effect of Counterions on the Structure and Stability of Aqueous Uranyl(VI) Complexes. A First-Principles Molecular Dynamics Study

Abstract: International audienc

Cited by 25 publications

References 18 publications

Molecular dynamics simulation study of distribution and dynamics of aqueous solutions of uranyl ions: the effect of varying temperature and concentration

Molecular dynamics simulation study of distribution and dynamics of aqueous solutions of uranyl ions: the effect of varying temperature and concentration

Combining luminescence spectroscopy, parallel factor analysis and quantum chemistry to reveal metal speciation – a case study of uranyl(vi) hydrolysis

Recent progress in actinide borate chemistry

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