Coordination and thermodynamic properties ...
Document type :
Compte-rendu et recension critique d'ouvrage
DOI :
Title :
Coordination and thermodynamic properties of aqueous protactinium(V) by first-principle calculations
Author(s) :
Oher, Hanna [Auteur]
Institut des Sciences Chimiques de Rennes [ISCR]
Laboratoire de physique subatomique et des technologies associées [SUBATECH]
Delafoulhouze, Jeremy [Auteur]
Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation [CEISAM]
Renault, Eric [Auteur]
Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation [CEISAM]
Vallet, Valérie [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Maurice, Rémi [Auteur correspondant]
Laboratoire de physique subatomique et des technologies associées [SUBATECH]
Institut des Sciences Chimiques de Rennes [ISCR]
Institut des Sciences Chimiques de Rennes [ISCR]
Laboratoire de physique subatomique et des technologies associées [SUBATECH]
Delafoulhouze, Jeremy [Auteur]
Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation [CEISAM]
Renault, Eric [Auteur]
Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation [CEISAM]
Vallet, Valérie [Auteur]
![refId](/themes/Mirage2//images/idref.png)
Physico-Chimie Moléculaire Théorique [PCMT]
Maurice, Rémi [Auteur correspondant]
Laboratoire de physique subatomique et des technologies associées [SUBATECH]
Institut des Sciences Chimiques de Rennes [ISCR]
Journal title :
Physical Chemistry Chemical Physics
Pages :
10033-10041
Publisher :
Royal Society of Chemistry
Publication date :
2023-01-20
ISSN :
1463-9076
HAL domain(s) :
Chimie/Chimie théorique et/ou physique
English abstract : [en]
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, ...
Show more >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 (SO<sub>4</sub><sup>2-</sup> and C<sub>2</sub>O<sub>4</sub><sup>2-</sup>, 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.Show less >
Show more >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 (SO<sub>4</sub><sup>2-</sup> and C<sub>2</sub>O<sub>4</sub><sup>2-</sup>, 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.Show less >
Language :
Anglais
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