Experimental and computational evidence of U(VI)-OH-Si(OH)4 complexes under alkaline conditions: Implications for cement systems.

The complexation of uranyl hydroxides with orthosilicic acid was investigated by experimental and theoretical methods. Spectroluminescence titration was performed in a glovebox under argon atmosphere at pH 9.2, 10.5 and 11.5, with [U(VI)] = 10-6 and 5 × 10-6 mol kgw-1. The polymerization effects of silicic acid were minimized by ruling out samples with less than 90 % monomeric silicic acid present, identified via UV-Vis spectrometry using the molybdate blue method. Linear regression analysis based on time-resolved laser-induced fluorescence spectroscopy (TRLFS) results yielded the conditional stepwise formation constants of U(VI)-OH-Si(OH)4 complexes at 0.05 mol kgw-1 NaNO3. The main spectroscopic features - characteristic peak positions and decay-time - are reported for the first time for the UO2(OH)2SiO(OH)3- species observed at pH 9.2 and 10.5 and UO2(OH)2SiO2(OH)22- predominant at pH 11.5. Quantum chemical calculations successfully computed the theoretical luminescence spectrum of the complex UO2(OH)2SiO(OH)3- species, thus underpinning the proposed chemical model for weakly alkaline systems. The conditional stability constants were extrapolated to infinite dilution using the Davies equation, resulting in log10ß°(UO2(OH)2SiO(OH)3-) and log10ß°(UO2(OH)2SiO2(OH)22-). Implications for U(VI) speciation in the presence and absence of competing carbonate are discussed for silicate-rich environments expected in certain repository concepts for nuclear waste disposal.

How Does Bending the Uranyl Unit Influence Its Spectroscopy and Luminescence?

Bent uranyl complexes can be formed with chloride ligands and 1,10-phenanthroline (phen) ligands bound to the equatorial and axial planes of the uranyl(VI) moiety, as revealed by the crystal structures, IR and Raman spectroscopy, and quantum-chemical calculations. With the goal of probing the influence of chloride and phenanthroline coordination enforcing the bending on the absorption and emission spectra of this complex, spin-orbit time-dependent density functional theory calculations for the bare uranyl complexes as well as for the free UO2Cl2 subunit and the UO2Cl2(phen)2 complex were performed. The emission spectra have been fully simulated by ab initio methods and compared to experimental photoluminescence spectra, recorded for the first time for UO2Cl2(phen)2. Notably, the bending of uranyl in UO2Cl2 and UO2Cl2(phen)2 triggers excitations of the uranyl bending mode, yielding a denser luminescence spectrum.

Coordination and thermodynamic properties of aqueous protactinium(V) by first-principle calculations.

Protactinium (Z = 91) is a very rare actinide with peculiar physico-chemical properties. Indeed, although one may naively think that it behaves similarly to either thorium or uranium by its position in the periodic table, it may in fact follow its own rules. Because of the quite small energy gap between its valence shells (in particular the 5f and 6d ones) and also the strong influence of relativistic effects on its properties, it is actually a challenging element for theoretical chemists. In this article, we combine experimental information, chemical arguments and standard first-principle calculations, complemented by implicit and explicit solvation, to revisit the stepwise complexation of aqueous protactinium(V) with sulfate and oxalate dianionic ligands (SO42- and C2O42-, respectively). From a methodological viewpoint, we notably conclude that it is necessary to at least saturate the coordination sphere of protactinium(V) to reach converged equilibrium constant values. Furthermore, in the case of single complexations (i.e. with one sulfate or oxalate ligand bound in the bidentate fashion), we show that it is necessary to maintain the coordination of one hydroxyl group, present in the supposed [PaO(OH)]2+ precursor, to obtain coherent complexation constants. Therefore, we predict that this hydroxyl group is maintained in the formation of 1 : 1 complexes while we confirm that it is withdrawn when coordinating three sulfate or oxalate ligands. Finally, we stress that this work is a first step toward the future use of theoretical predictions to elucidate the enigmatic chemistry of protactinium in solution.

Influence of the First Coordination of Uranyl on Its Luminescence Properties: A Study of Uranyl Binitrate with N,N-Dialkyl Amide DEHiBA and Water.

Uranyl binitrate complexes have a particular interest in the nuclear industry, especially in the reprocessing of spent nuclear fuel. The modified PUREX extraction process is designed to extract U(VI) in the form of UO2(NO3)2(L)2 as has been confirmed by extended X-ray absorption fine structure (EXAFS), X-ray diffraction (XRD), and time-resolved laser-induced fluorescence spectroscopy (TRLFS) measurements. In this study, the L ligands are two molecules of N,N-di-(ethyl-2-hexyl)isobutyramide (DEHiBA) monoamide used to bind uranyl in its first coordination sphere. DEHiBA ligands can coordinate uranyl in either trans- or cis-position with respect to the nitrate ligands, and these two conformers may coexist in solution. To use luminescence spectroscopy as a speciation technique, it is important to determine whether or not these conformers can be discriminated by their spectroscopic properties. To answer this question, the spectra of trans- and cis-UO2(NO3)2(DEiBA)2 conformers were modeled with ab initio methods and compared to the experimental time-resolved luminescence spectra on UO2(NO3)2(DEHiBA)2 systems. Moreover, the hydrated uranyl binitrate UO2(NO3)2(H2O)2 complexes in the same trans and cis configurations were modeled to quantify the impact of organic DEHiBA on the luminescence properties.

Influence of Alkaline Earth Metal Ions on Structures and Luminescent Properties of NamMnUO2(CO3)3(4-m-2n)- (M = Mg, Ca; m, n = 0-2): Time-Resolved Fluorescence Spectroscopy and Ab Initio Studies.

The luminescence spectra of triscarbonatouranyl complexes were determined by experimental and theoretical methods. Time-resolved laser-induced fluorescence spectroscopy was used to monitor spectra of uranyl and bicarbonate solutions at 0.1 mol kgw-1 ionic strength and pH ca. 8. The concentrations of Mg2+ and Ca2+ in the samples were chosen in order to vary the proportions of the alkaline earth ternary uranyl complexes MgUO2(CO3)32-, CaUO2(CO3)32-, and Ca2UO2(CO3)3. The luminescence spectrum of each complex was determined by decomposition in order to compare it with the simulated spectra of model structures NamMnUO2(CO3)3(4-m-2n)- (M = Mg, Ca; m, n = 0-2) obtained by quantum chemical methods. The density functional theory (DFT) and time-dependent (TD)-DFT methods were used with the PBE0 functional to optimize the structures in the ground and excited states, respectively, including relativistic effects at the spin-free level, and water solvent effects using a continuum polarizable conductor model. The changes in the structural parameters were quantified with respect to the nature and the amount of alkaline earth counterions to explain the luminescence spectra behavior. The first low-lying excited state was successfully computed, together with the vibrational harmonic frequencies. The DFT calculations confirmed that uranyl luminescence originates from electronic transitions from one of the four nonbonding 5f orbitals of uranium to an orbital that has a uranyl-σ (5f, 6d) character mixed with the 2p atomic orbitals of the carbonate oxygens. Additional single-point calculations using the more accurate TD-DFT/CAM-B3LYP allow one to determine the position of the luminescence "hot band" for each structure in the range 467-476 nm and compared fairly well with experimental reports at around 465 nm. The complete luminescence spectra were built from theoretical results with the corresponding assignment of the electronic transitions and vibronic modes involved, mainly the U-Oax stretching mode. The resulting calculated spectra showed a very good agreement with experimental band positions and band spacing attributed to MgUO2(CO3)32-, CaUO2(CO3)32-, and Ca2UO2(CO3)3. The evolution of luminescence intensities with the number of alkaline earth metal ions in the structure was also correctly reproduced.

Investigation of the Luminescence of [UO2X4]2- (X = Cl, Br) Complexes in the Organic Phase Using Time-Resolved Laser-Induced Fluorescence Spectroscopy and Quantum Chemical Simulations.

The luminescence properties of the [UO2Cl4]2- complex in an organic phase, especially the influence of large organic countercations, have been studied by time-resolved laser-induced fluorescence spectroscopy (TRLFS) and ab initio modeling. The experimental spectrum was assigned by vibronic Franck-Condon calculations on quantum chemical methods on the basis of a combination of relativistic density functional approaches. The shape of the luminescence spectrum of the uranyl tetrachloride complex is determined by symmetrical vibrations and geometrical change upon emission. The possible change in the luminescence properties depending on the first and second uranyl coordination spheres was predicted theoretically for the [UO2Br4]2- and [R4N]2[UO2Cl4] ([R4N] = [Bu4N], [A336]) systems. The computations reveal that, for U(VI), the second coordination sphere has little influence on the spectrum shape, making speciation of uranyl complexes with identical first-coordination-sphere ligands tedious to discriminate. The computed structural changes agreed well with experimental trends; theoretical spectra and peak attributions are in good accordance with TRLFS and magnetic circular dichroism (MCD) data, respectively.