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 [(An^VO₂)(CH₃SO₂)₂]^- or [(An^VO₂)(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).