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

Autor: Hanna Oher, Jérémy Delafoulhouze, Eric Renault, Valérie Vallet, Rémi Maurice
Přispěvatelé: Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique subatomique et des technologies associées (SUBATECH), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), This work was supported by the Région des Pays de la Loire (RCT-PaPAn project) and by the French National Research Agency (ANR-21-CE29-0027, LABEX CaPPA/ANR-11-LABX-0005-01 and I-SITE ULNE/ANR-16-IDEX-0004 ULNE). HPC resources from CCIPL (Centre de Calcul Intensif des Pays de la Loire) were used., ANR-21-CE29-0027,CHESS,Chimie, spectroscopie et spéciation du protactinium(2021), ANR-16-IDEX-0004,ULNE,ULNE(2016), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011)
Rok vydání: 2023
Předmět:
Zdroj: Physical Chemistry Chemical Physics
Physical Chemistry Chemical Physics, 2023, 25, pp.10033-10041. ⟨10.1039/D3CP00323J⟩
ISSN: 1463-9084
1463-9076
DOI: 10.1039/d3cp00323j
Popis: International audience; 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, thought of in the [PaO(OH)]^3+ 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.
Databáze: OpenAIRE
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