Solvation of UCl62− Anionic Complex by MeBu3N+, BuMe2Im+, and BuMeIm+ Cations

Bossé, Emilie; Auwer, Christophe Den; Berthon, Christophe; Guilbaud, Philippe; Grigoriev, Mikhail S.; Nikitenko, Sergei I.; Naour, C. Le; Cannes, Céline; Moisy, Philippe

doi:10.1021/ic702477z

Cited by 36 publications

(38 citation statements)

References 31 publications

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“…The trend of the calculated gas phase U-Cl bond lengths is consistent with the experimental values measured in the condensed phase. [77][78][79][80][81][82][83] In particular, for UCl 6 2− , the counterions in the crystal lattice counterbalance the strong Coulomb repulsion between the Cl − ions, resulting in shorter R(U-Cl) values than in vacuum. The geometric and electronic structures are reasonably reproduced by the DFT approximation, which gives confidence in the calculated (harmonic) symmetric stretching vibrational frequencies.…”

Section: Theoretical Resultsmentioning

confidence: 99%

Photoelectron spectroscopy and theoretical studies of gaseous uranium hexachlorides in different oxidation states: UCl6q− (q = 0–2)

Dau

Liu

et al. 2015

The Journal of Chemical Physics

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Uranium chlorides are important in actinide chemistry and nuclear industries, but their chemical bonding and many physical and chemical properties are not well understood yet. Here, we report the first experimental observation of two gaseous uranium hexachloride anions, UCl6 (-) and UCl6 (2-), which are probed by photoelectron spectroscopy in conjunction with quantum chemistry calculations. The electron affinity of UCl6 is measured for the first time as +5.3 eV; its second electron affinity is measured to be +0.60 eV from the photoelectron spectra of UCl6 (2-). We observe that the detachment cross sections of the 5f electrons are extremely weak in the visible and UV energy ranges. It is found that the one-electron one-determinental molecular orbital picture and Koopmans' theorem break down for the strongly internally correlated U-5f(2) valence shell of tetravalent U(+4) in UCl6 (2-). The calculated adiabatic and vertical electron detachment energies from ab initio calculations agree well with the experimental observations. Electronic structure and chemical bonding in the uranium hexachloride species UCl6 (2-) to UCl6 are discussed as a function of the oxidation state of U.

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Section: Theoretical Resultsmentioning

confidence: 99%

Photoelectron spectroscopy and theoretical studies of gaseous uranium hexachlorides in different oxidation states: UCl6q− (q = 0–2)

Dau

Liu

et al. 2015

The Journal of Chemical Physics

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“…For comparison, literature data of experimentally derived bond lengths are also included. Where experimental data exists [20,21], M-Cl bond lengths appear to be ~0.02 Å longer in the aqueous phase than in the solid state and, bearing in mind that a continuum solvation model is employed here, it might be expected that theoretical results would be in better agreement with aqueous phase data. All methodologies reproduce XRD-derived bond lengths with high accuracy in the closed shell U(VI) complex, whereas there is slight overestimation in the U(V) complex.…”

Section: Structural Characterisationmentioning

confidence: 88%

Assessing Covalency in Cerium and Uranium Hexachlorides: A Correlated Wavefunction and Density Functional Theory Study

Beekmeyer

Kerridge

2015

Inorganics

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The electronic structure of a series of uranium and cerium hexachlorides in a variety of oxidation states was evaluated at both the correlated wavefunction and density functional (DFT) levels of theory. Following recent experimental observations of covalency in tetravalent cerium hexachlorides, bonding character was studied using topological and integrated analysis based on the quantum theory of atoms in molecules (QTAIM). This analysis revealed that M-Cl covalency was strongly dependent on oxidation state, with greater covalency found in higher oxidation state complexes. Comparison of M-Cl delocalisation indices revealed a discrepancy between correlated wavefunction and DFT-derived values. Decomposition of these delocalisation indices demonstrated that the origin of this discrepancy lay in ungerade contributions associated with the f-manifold which we suggest is due to self-interaction error inherent to DFT-based methods. By all measures used in this study, extremely similar levels of covalency between complexes of U and Ce in the same oxidation state was found.

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“…For chloride ions, Nikitenko et al and Bossé et al investigated the complex by dissolving [BMIm] 2 [UCl 6 ], [MeBu 3 N] 2 [UCl 6 ] (MeBu 3 N = methyltributylammonium), and [BuMe 2 Im] 2 [UCl 6 ] (BuMe 2 Im = 1‐butyl‐2,3‐dimethylimidazolium) in the related Tf 2 N − ‐based ionic liquids and proved that the octahedral structure of [UCl 6 ] 2− remained unchanged even without further addition of Cl − . For UO 2 2+ as a source of uranium, its interaction with Cl − was systematically studied by Gaillard group.…”

Section: Determination Of Actinide Speciation By Xafsmentioning

confidence: 99%

Exploring Actinide Materials Through Synchrotron Radiation Techniques

et al. 2014

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Synchrotron radiation (SR) based techniques have been utilized with increasing frequency in the past decade to explore the brilliant and challenging sciences of actinide‐based materials. This trend is partially driven by the basic needs for multi‐scale actinide speciation and bonding information and also the realistic needs for nuclear energy research. In this review, recent research progresses on actinide related materials by means of various SR techniques were selectively highlighted and summarized, with the emphasis on X‐ray absorption spectroscopy, X‐ray diffraction and scattering spectroscopy, which are powerful tools to characterize actinide materials. In addition, advanced SR techniques for exploring future advanced nuclear fuel cycles dealing with actinides are illustrated as well.

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Solvation of UCl₆²⁻ Anionic Complex by MeBu₃N⁺, BuMe₂Im⁺, and BuMeIm⁺ Cations

Cited by 36 publications

References 31 publications

Photoelectron spectroscopy and theoretical studies of gaseous uranium hexachlorides in different oxidation states: UCl6q− (q = 0–2)

Photoelectron spectroscopy and theoretical studies of gaseous uranium hexachlorides in different oxidation states: UCl6q− (q = 0–2)

Assessing Covalency in Cerium and Uranium Hexachlorides: A Correlated Wavefunction and Density Functional Theory Study

Exploring Actinide Materials Through Synchrotron Radiation Techniques

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