Theoretical unraveling of the separation of trivalent Am and Eu ions by phosphine oxide ligands with different central heterocyclic moieties

Abstract

The treatment of nuclear spent fuels, especially the separation of minor actinides, is an imperative task for the healthy development of the nuclear industry. Up to now, it still remains a worldwide challenge to separate trivalent An³⁺ from Ln³⁺ because of their similar chemical properties. Therefore, investigating the mechanism behind the selective extraction of An³⁺ by theoretical methods is necessary. In this work, three phosphine oxide ligands with the same side structures but different bridging frameworks, Ph₂PyPO, Ph₂BipyPO and Ph₂PhenPO, were investigated theoretically, and compared with each other using relativistic density functional theory. The results of QTAIM and MBO suggest that the Am–N bonds in the studied complexes have more covalent character than those in the Eu–N bonds, whereas the PDOS analysis indicates that more overlap exists between Am-5f and the Ph₂PyPO's N-2p orbital than between Am-5f and Ph₂BipyPO's N-2p, and Am-5f and Ph₂PhenPO's N-2p orbital. However, the studied ligands all possess stronger affinities towards Am³⁺ than Eu³⁺, which partly results in the Am³⁺ selectivity towards Eu³⁺ in these three ligands. The calculated reaction free energy can reproduce the Am/Eu separation ability difference of three ligands well. This work offers some useful information for An/Ln separation of phosphine oxide ligands, and may help to design more efficient An³⁺/Ln³⁺ separation ligands.