Electronic structure of uranyl complexes ...
Type de document :
Autre communication scientifique (congrès sans actes - poster - séminaire...): Communication dans un congrès avec actes: Conférence invitée
Titre :
Electronic structure of uranyl complexes probed by valence and X-ray spectroscopy
Auteur(s) :
Vallet, Valérie [Orateur]
Physico-Chimie Moléculaire Théorique [PCMT]
Misael, Wilken [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Oher, Hanna [Auteur]
Institut des Sciences Chimiques de Rennes [ISCR]
Wilson, Richard [Auteur]
Chemical Sciences and Engineering Division [Argonne]
Severo Pereira Gomes, Andre [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Physico-Chimie Moléculaire Théorique [PCMT]
Misael, Wilken [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Oher, Hanna [Auteur]
Institut des Sciences Chimiques de Rennes [ISCR]
Wilson, Richard [Auteur]
Chemical Sciences and Engineering Division [Argonne]
Severo Pereira Gomes, Andre [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Titre de la manifestation scientifique :
2024 MRS Spring Meeting
Ville :
Seattle
Pays :
Etats-Unis d'Amérique
Date de début de la manifestation scientifique :
2024-04-22
Date de publication :
2024-04-22
Discipline(s) HAL :
Chimie/Chimie théorique et/ou physique
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
Résumé en anglais : [en]
This presentation will showcase the capabilities of relativistic quantum chemistry approaches in exploring the electronic structure of actinide-containing compounds. The focus will be on luminescence properties and core-level ...
Lire la suite >This presentation will showcase the capabilities of relativistic quantum chemistry approaches in exploring the electronic structure of actinide-containing compounds. The focus will be on luminescence properties and core-level spectroscopic observables of the uranyl moiety (UO<sub>2</sub><sup>2+</sup>) within both linear and bent uranyl complexes. Given the challenges associated with nuclear waste management and the environmental impact of fission products, efficient extraction and characterization methods for actinide-containing compounds are of great societal importance.<br><br>The electronic structure of actinide compounds remains poorly understood compared to other elements in the periodic table. Valence- and core-level spectroscopic techniques offer valuable insights into this complex subject. The presentation will demonstrate how luminescence spectroscopy and X-ray spectroscopies serve as sensitive tools for probing the electronic structure and bonding nature between the uranyl moiety and its coordinated ligands.<br><br>Specifically, the talk will cover the application of relativistic Time-Dependent Density Functional Theory (TDDFT) with the CAM-B3LYP functional. This method has proven effective in providing accurate excitation/emission energies and vibronic progressions for linear uranyl complexes (UO<sub>2</sub>Cl<sub>4</sub><sup>2-</sup>, UO<sub>2</sub>F<sub>5</sub><sup>3-</sup>, UO<sub>2</sub>(CO<sub>3</sub>)<sub>2</sub><sup>4-</sup>, UO<sub>2</sub>(NO<sub>3</sub>)L<sub>2</sub>), enabling the assignment of experimental data [1]. Additionally, the impact of bending the uranyl moiety on spectroscopy and observed vibronic progressions will be discussed [2].<br><br>The presentation will also delve into TD-DFT simulations of the core spectra of the uranyl tetrachloride dianion (UO<sub>2</sub>Cl<sub>4</sub><sup>2-</sup>) in the Cs<sub>2</sub>UO<sub>2</sub>Cl<sub>4</sub> crystal. These simulations align with previously reported angle-resolved near-edge X-ray absorption spectroscopy (NEXAFS) at the oxygen K-edge and high-energy resolution fluorescence detected (HERFD-XANES) at the uranium M<sub>4</sub>- and L<sub>3</sub>-edges [3].<br><br>[1] H. Oher et al. <i>Inorg. Chem.</i> <b>2020</b>, <i>59</i> 5896; H. Oher et al. <i>Inorg. Chem.</i> <b>2020</b>, <i>59</i>, 15036; H. Oher et al. <i>Inorg. Chem.</i> <b>2022</b>, <i>61</i>, 890.<br>[2] H. Oher et al. <i>Inorg. Chem.</i> <b>2023</b>, <i>62</i>, 9273–9284.<br>[3] W. A. Misael, A. S. P. Gomes, <i>Inorg. Chem.</i> <b>2023</b>, <i>62</i>, 11589–11601.<br>Lire moins >
Lire la suite >This presentation will showcase the capabilities of relativistic quantum chemistry approaches in exploring the electronic structure of actinide-containing compounds. The focus will be on luminescence properties and core-level spectroscopic observables of the uranyl moiety (UO<sub>2</sub><sup>2+</sup>) within both linear and bent uranyl complexes. Given the challenges associated with nuclear waste management and the environmental impact of fission products, efficient extraction and characterization methods for actinide-containing compounds are of great societal importance.<br><br>The electronic structure of actinide compounds remains poorly understood compared to other elements in the periodic table. Valence- and core-level spectroscopic techniques offer valuable insights into this complex subject. The presentation will demonstrate how luminescence spectroscopy and X-ray spectroscopies serve as sensitive tools for probing the electronic structure and bonding nature between the uranyl moiety and its coordinated ligands.<br><br>Specifically, the talk will cover the application of relativistic Time-Dependent Density Functional Theory (TDDFT) with the CAM-B3LYP functional. This method has proven effective in providing accurate excitation/emission energies and vibronic progressions for linear uranyl complexes (UO<sub>2</sub>Cl<sub>4</sub><sup>2-</sup>, UO<sub>2</sub>F<sub>5</sub><sup>3-</sup>, UO<sub>2</sub>(CO<sub>3</sub>)<sub>2</sub><sup>4-</sup>, UO<sub>2</sub>(NO<sub>3</sub>)L<sub>2</sub>), enabling the assignment of experimental data [1]. Additionally, the impact of bending the uranyl moiety on spectroscopy and observed vibronic progressions will be discussed [2].<br><br>The presentation will also delve into TD-DFT simulations of the core spectra of the uranyl tetrachloride dianion (UO<sub>2</sub>Cl<sub>4</sub><sup>2-</sup>) in the Cs<sub>2</sub>UO<sub>2</sub>Cl<sub>4</sub> crystal. These simulations align with previously reported angle-resolved near-edge X-ray absorption spectroscopy (NEXAFS) at the oxygen K-edge and high-energy resolution fluorescence detected (HERFD-XANES) at the uranium M<sub>4</sub>- and L<sub>3</sub>-edges [3].<br><br>[1] H. Oher et al. <i>Inorg. Chem.</i> <b>2020</b>, <i>59</i> 5896; H. Oher et al. <i>Inorg. Chem.</i> <b>2020</b>, <i>59</i>, 15036; H. Oher et al. <i>Inorg. Chem.</i> <b>2022</b>, <i>61</i>, 890.<br>[2] H. Oher et al. <i>Inorg. Chem.</i> <b>2023</b>, <i>62</i>, 9273–9284.<br>[3] W. A. Misael, A. S. P. Gomes, <i>Inorg. Chem.</i> <b>2023</b>, <i>62</i>, 11589–11601.<br>Lire moins >
Langue :
Anglais
Comité de lecture :
Oui
Audience :
Internationale
Vulgarisation :
Non
Projet ANR :
Source :