Study of kinetic electrolyte effects on a fast reaction in solution: The quenching of fluorescence of uranyl ion up to high electrolyte concentration

Simonin, Jean‐Pierre; Billard, Isabelle; Hendrawan, Hendrawan; Bernard, Olivier; Lützenkirchen, K.; Sémon, Laurent

doi:10.1039/b210838k

Cited by 11 publications

(10 citation statements)

References 39 publications

(72 reference statements)

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“…The experimental self-diffusion coefficient for [UO 2 ] 2+ at infinite dilution is (0.67 ± 0.01) 10 −5 cm 2 s 1 . 89,90 The simulated value only has the right order of magnitude of the experimental. The TIP4P water model overestimates the self-diffusion coefficient of water by ∼50%; therefore since the water molecules around the cation move too fast, the cation is more free to move than if the water dynamics was more accurate.…”

Section: Self-diffusion Coefficientmentioning

confidence: 92%

A hydrated ion model of [UO2]2+ in water: Structure, dynamics, and spectroscopy from classical molecular dynamics

Pérez-Conesa

Torrico

Martı́nez

et al. 2016

The Journal of Chemical Physics

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A new ab initio interaction potential based on the hydrated ion concept has been developed to obtain the structure, energetics, and dynamics of the hydration of uranyl in aqueous solution. It is the first force field that explicitly parameterizes the interaction of the uranyl hydrate with bulk water molecules to accurately define the second-shell behavior. The [UO(HO)] presents a first hydration shell U-O average distance of 2.46 Å and a second hydration shell peak at 4.61 Å corresponding to 22 molecules using a coordination number definition based on a multisite solute cavity. The second shell solvent molecules have longer mean residence times than those corresponding to the divalent monatomic cations. The axial regions are relatively de-populated, lacking direct hydrogen bonding to apical oxygens. Angle-solved radial distribution functions as well as the spatial distribution functions show a strong anisotropy in the ion hydration. The [UO(HO)] solvent structure may be regarded as a combination of a conventional second hydration shell in the equatorial and bridge regions, and a clathrate-like low density region in the axial region. Translational diffusion coefficient, hydration enthalpy, power spectra of the main vibrational modes, and the EXAFS spectrum simulated from molecular dynamics trajectories agree fairly well with the experiment.

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Section: Self-diffusion Coefficientmentioning

confidence: 92%

A hydrated ion model of [UO2]2+ in water: Structure, dynamics, and spectroscopy from classical molecular dynamics

Pérez-Conesa

Torrico

Martı́nez

et al. 2016

The Journal of Chemical Physics

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“…The experimental self diffusion coefficients of the different actinyls range from 0.55 × 10 −5 cm 2 s −1 to 0.8 × 10 −5 cm 2 s −1 . [64][65][66] Considering TIP4P water mobility is too high, the aqua ion translates more freely than it should as well. The normalization corrects this effect, and then the data agree within the error with the experimental normalized range, 0.24-0.35, 64,65 using 2.3 × 10 −5 cm 2 s −1 for water.…”

Section: B Self-diffusion Coefficientmentioning

confidence: 99%

A general study of actinyl hydration by molecular dynamics simulations using ab initio force fields

Pérez-Conesa

Torrico

Martı́nez

et al. 2019

The Journal of Chemical Physics

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A set of new ab initio force fields for aqueous [AnO 2 ] 2+/+ (An = Np(VI,V), Pu(VI), Am(VI)) has been developed using the Hydrated Ion (HI) model methodology previously used for [UO 2 ] 2+ . Except for the non-electrostatic contribution of the HI-bulk water interaction, the interaction potentials are individually parameterized. Translational diffusion coefficients, hydration enthalpies, and vibrational normal mode frequencies were calculated from the MD simulations. Physico-chemical properties satisfactorily agree with experiments validating the robustness of the force field strategy. The solvation dynamics and structure for all hexavalent actinoids are extremely similar and resemble our previous analysis of the uranyl cation. This supports the idea of using the uranyl cation as a reference for the study of other minor actinyls. The comparison between the NpO 2+ 2 and NpO + 2 hydration only provides significant differences in first and second shell distances and second-shell mean residence times. We propose a single general view of the [AnO 2 ] 2+/+ hydration structure: aqueous actinyls are amphiphilic anisotropic solutes which are equatorially conventional spherically symmetric cations capped at the poles by clathrate-like water structures.

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“…For both metal ions the experimentally determined quenching constant is much lower than the calculated value, implying that the energy transfer process in water cannot be described by a diffusion controlled reaction although diffusion controlled quenching processes have been evidenced for UO 2 2+ in water. 44, 45 As a partial conclusion it can be said that in aqueous solution the coordination (solvation chemistry) as well as the reactivity (solution chemistry) of the lanthanide Eu(III) and the actinide Cm(III) are similar.…”

Section: Eu(iii) and Cm(iii) Fluorescence Quenching In Aqueous Solutionmentioning

confidence: 99%

Differences of Eu(iii) and Cm(iii) chemistry in ionic liquids: investigations by TRLFS

et al. 2007

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In this study the coordination structure and chemistry of Eu(III) and Cm(III) in the ionic liquid C(4)mimTf(2)N (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) was investigated by time-resolved laser fluorescence spectroscopy (TRLFS). The dissolution of 1 x 10(-2) M Eu(CF(3)SO(3))(3) and 1 x 10(-7) M Cm(ClO(4))(3) in C(4)mimTf(2)N leads to the formation of two species for each cation with fluorescence emission lifetimes of 2.5 +/- 0.2 ms and 1.0 +/- 0.3 ms for the Eu-species and 1.0 +/- 0.3 ms and 300.0 +/- 50 micros for the Cm-species. The interpretation of the TRLFS data indicates a comparable coordination for both the lanthanide and actinide cation in this ionic liquid. The quenching influence of Cu(II) on the fluorescence emission of Eu(III) and Cm(III) was also measured by TRLFS. While Cu(ii) does not quench the Cm(III) fluorescence emission in C(4)mimTf(2)N the Eu(III) fluorescence emission lifetime for both Eu-species in C(4)mimTf(2)N decreases with increasing Cu(II) concentration. Stern-Volmer constants were calculated (k(SV) = 1.54 x 10(6) M(-1) s(-1) and k(SV) = 2.70 x 10(6) M(-1)). By contrast, the interaction of Cu(II) with Eu(III) and Cm(III) in water leads to a quenching of both the lanthanide and actinide fluorescence. The calculated Stern-Volmer constants are 1.20 x 10(4) M(-1) s(-1) for Eu(III) and 1.27 x 10(4) M(-1) s(-1) for Cm(III). The investigations show, while the chemistry of trivalent lanthanides and actinides is similar in an aqueous system it is dramatically different in ionic liquids. This difference in chemical behavior may provide the opportunity for a separation of lanthanides and actinides with regard to the reprocessing of nuclear fuel.

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Study of kinetic electrolyte effects on a fast reaction in solution: The quenching of fluorescence of uranyl ion up to high electrolyte concentration

Cited by 11 publications

References 39 publications

A hydrated ion model of [UO2]2+ in water: Structure, dynamics, and spectroscopy from classical molecular dynamics

A hydrated ion model of [UO2]2+ in water: Structure, dynamics, and spectroscopy from classical molecular dynamics

A general study of actinyl hydration by molecular dynamics simulations using ab initio force fields

Differences of Eu(iii) and Cm(iii) chemistry in ionic liquids: investigations by TRLFS

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