Challenges in relativistic electronic structure calculations of gas-phase reactivity and thermodynamics of actinide species
| Autor: | Vallet, Valérie, Réal, Florent, Severo Pereira Gomes, André, Kervazo, Sophie, Saab, Mohamad, Virot, François, Gong, Yu, Gibson, John K. |
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| Přispěvatelé: | 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), Pôle Sûreté Nucléaire - Recherche en sûreté (IRSN/PSN-RES), Institut de Radioprotection et de Sûreté Nucléaire (IRSN), Chemical Sciences Division [LBNL Berkeley] (CSD), Lawrence Berkeley National Laboratory [Berkeley] (LBNL), CPER CLIMIBIO, ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), ANR-16-IDEX-0004,ULNE,ULNE(2016), Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille, PSN-RES, ANR: 11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011) |
| Jazyk: | angličtina |
| Rok vydání: | 2022 |
| Předmět: | |
| Zdroj: | Plutonium Futures: The Science 2022 Plutonium Futures: The Science 2022, Sep 2022, Avignon, France Plutonium Futures 2020 Plutonium Futures 2020, Jun 2020, Montpellier, France International Workshop on Theory Frontiers in Actinide Sciences: Chemistry and Materials International Workshop on Theory Frontiers in Actinide Sciences: Chemistry and Materials, Feb 2020, Santa Fe, United States |
| Popis: | International audience; Probing the electronic structures, reactivity and thermodynamics properties of early actinide (U, Np, Pu) elements is a key fundamental aspect of actinide physical-chemistry, in order to elucidate to which extent their properties differ from one element to the other. When studied in the gas phase, it is possible to probe oxidation states that might not be readily accessible in condensed phase.In this presentation, we will first discuss the reactivity of pentavalent actinyl AnO2(V) sulfinate complexes [(AnVO2)(CH3SO2)2]- or [(AnVO2)(C6H5SO2)2]- to investigate on the one side how Np and Pu complexes might differ from U ones, and on the other side, how the relative strengths of C-S bond in methanesulfinate and benzesulftinate impact the fragmentation pathways. To answer these question, we have confronted the results of collision induced dissociation experiments to relativistic multi-reference electronic structure calculations [1].The second focus will be on the thermodynamics properties of gas-phase volatile plutonium species, PuO2, PuO3, and PuO2(OH)2, in their neutral and ionic forms. We showcase the use of relativistic quantum chemical methods to predict the forms and quantities of the released plutonium species under accidental conditions [2, 3].[1] V. Vallet, Y. Gong, M. Saab, F. Réal, J. K. Gibson, submitted to Dalton Trans.[2] K. Boguslawski, F. Réal, P. Tecmer, C. Duperrouzel, A. S. P. Gomes, Ö. Legeza, P. W. Ayers, and V. Vallet, Phys. Chem. Chem. Phys. 19, 4317 (2017)[3] S. Kervazo, F. Réal, F. Virot, A. S. P. Gomes, V. Vallet, Inorg. Chem. 58, 14507–14521 (2019). |
| Databáze: | OpenAIRE |
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