Work

Electronic structure of molybdenum chalcogenide clusters as supports for low-valent actinides

Year: 2025

Type: article

Abstract: chalcogenide clusters with early actinides were studied using density functional theory and multireference methodologies. We confirmed that the incorporation of low-valent U(III) leads to its oxidation to U(IV) due to an intramolecular redox reaction with the molybdenum sulfide core. On the contrary, open questions remain with respect to the oxidation state of low-valent transuranic elements upon their coordination to the molybdenum sulfide core. Density functional theory calculations indicate that the transuranic center remains An(III), while complete active space calculations suggest an actinide oxidation analogous to the one observed in the uranium species. The predominantly electrostatic bonding between the actinides and the molybdenum sulfide cluster was assigned using the quantum theory of atoms in molecules. Our results on clusters with harder and softer chalcogenides are in agreement with a preferential soft-soft interaction between the actinide and its support.

Source: Dalton Transactions

DOI: 10.1039/d4dt02911a

Authors: Pere Miró, S. Genevieve Duggan

Institutions: University of Iowa, University of South Dakota

Language: English

Topic: Radioactive element chemistry and processing

Subfield: Inorganic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Funders: National Science Foundation, University of South Dakota

Awards: MRI: Acquisition of the Lawrence Supercomputer to Advance Multidisciplinary Research in South Dakota, G6884065497