Stability of the protactinium(V) mono-oxo ...
Type de document :
Compte-rendu et recension critique d'ouvrage
DOI :
PMID :
Titre :
Stability of the protactinium(V) mono-oxo cation probed by first-principle calculations
Auteur(s) :
Shaaban, Tamara [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Réal, Florent [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Maurice, Rémi [Auteur]
Institut des Sciences Chimiques de Rennes [ISCR]
Vallet, Valérie [Auteur correspondant]
Physico-Chimie Moléculaire Théorique [PCMT]
Physico-Chimie Moléculaire Théorique [PCMT]
Réal, Florent [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Maurice, Rémi [Auteur]
Institut des Sciences Chimiques de Rennes [ISCR]
Vallet, Valérie [Auteur correspondant]
Physico-Chimie Moléculaire Théorique [PCMT]
Titre de la revue :
Chemistry - a European Journal
Pagination :
e202304068
Éditeur :
Wiley-VCH Verlag
Date de publication :
2024
ISSN :
0947-6539
Mot(s)-clé(s) en anglais :
Protactinium
Quantum Chemistry
Solvation
Bond analysis
Coordination Chemistry
Quantum Chemistry
Solvation
Bond analysis
Coordination Chemistry
Discipline(s) HAL :
Chimie/Chimie théorique et/ou physique
Chimie/Chimie de coordination
Chimie/Radiochimie
Chimie/Chimie de coordination
Chimie/Radiochimie
Résumé en anglais : [en]
This study explores the distinctive behavior of Protactinium (Z = 91) within the actinide series. In contrast to neighboring elements like uranium or plutonium, Protactinium in the pentavalent state diverges by not forming ...
Lire la suite >This study explores the distinctive behavior of Protactinium (Z = 91) within the actinide series. In contrast to neighboring elements like uranium or plutonium, Protactinium in the pentavalent state diverges by not forming the typical dioxo pro- tactinyl moiety PaO<sub>2</sub><sup>+</sup>. Instead, it manifests as a monooxo PaO<sup>3+</sup> cation. Employing first-principle calculations with implicit and explicit solvation, we investigate two sto- ichiometrically equivalent neutral complexes: PaO(OH)<sub>2</sub>(X)(H<sub>2</sub>O) and Pa(OH)<sub>4</sub>(X), where X represents various monodentate and bidentate ligands. Calculating the Gibbs’ free energy for the reaction PaO(OH)<sub>2</sub>(X)(H<sub>2</sub>O) → Pa(OH)<sub>4</sub>(X), we find that the PaO(OH)<sub>2</sub>(X)(H<sub>2</sub>O) complex is stabilized with Cl<sup>–</sup> , Br<sup>–</sup> , I<sup>–</sup> , NCS<sup>–</sup> , NO<sub>3</sub><sup>–</sup>, and SO<sub>4</sub><sup>2–</sup> ligands, while it is not favored with OH<sup>–</sup>, F<sup>–</sup>, and C<sub>2</sub>O<sub>4</sub><sup>2–</sup> ligands. Quantum Theory of Atoms in Molecules (QTAIM) and Natural Bond Orbital (NBO) methods reveal the Pa mono-oxo bond as a triple bond, with significant contributions from the 5f and 6d shells. Covalency of the Pa mono-oxo bond increases with certain ligands, such as Cl<sup>–</sup>, Br<sup>–</sup>, I<sup>–</sup>, NCS<sup>–</sup>, and NO<sub>3</sub><sup>–</sup>. These findings elucidate Protactinium’s unique chemical attributes and provide insights into the conditions supporting the stability of relevant complexes.Lire moins >
Lire la suite >This study explores the distinctive behavior of Protactinium (Z = 91) within the actinide series. In contrast to neighboring elements like uranium or plutonium, Protactinium in the pentavalent state diverges by not forming the typical dioxo pro- tactinyl moiety PaO<sub>2</sub><sup>+</sup>. Instead, it manifests as a monooxo PaO<sup>3+</sup> cation. Employing first-principle calculations with implicit and explicit solvation, we investigate two sto- ichiometrically equivalent neutral complexes: PaO(OH)<sub>2</sub>(X)(H<sub>2</sub>O) and Pa(OH)<sub>4</sub>(X), where X represents various monodentate and bidentate ligands. Calculating the Gibbs’ free energy for the reaction PaO(OH)<sub>2</sub>(X)(H<sub>2</sub>O) → Pa(OH)<sub>4</sub>(X), we find that the PaO(OH)<sub>2</sub>(X)(H<sub>2</sub>O) complex is stabilized with Cl<sup>–</sup> , Br<sup>–</sup> , I<sup>–</sup> , NCS<sup>–</sup> , NO<sub>3</sub><sup>–</sup>, and SO<sub>4</sub><sup>2–</sup> ligands, while it is not favored with OH<sup>–</sup>, F<sup>–</sup>, and C<sub>2</sub>O<sub>4</sub><sup>2–</sup> ligands. Quantum Theory of Atoms in Molecules (QTAIM) and Natural Bond Orbital (NBO) methods reveal the Pa mono-oxo bond as a triple bond, with significant contributions from the 5f and 6d shells. Covalency of the Pa mono-oxo bond increases with certain ligands, such as Cl<sup>–</sup>, Br<sup>–</sup>, I<sup>–</sup>, NCS<sup>–</sup>, and NO<sub>3</sub><sup>–</sup>. These findings elucidate Protactinium’s unique chemical attributes and provide insights into the conditions supporting the stability of relevant complexes.Lire moins >
Langue :
Anglais
Vulgarisation :
Non
Projet ANR :
Source :
Fichiers
- stability-of-the-protactinium-v-mono-oxo-cation-probed-by-first-principle-calculations.pdf
- Accès libre
- Accéder au document
- document
- Accès libre
- Accéder au document
- ms-arxiv-Pa5p-PaO-cmplx.pdf
- Accès libre
- Accéder au document