Density Functional Theory Investigations on the Mechanism of Formation of Pa(V) Ion in Hydrous Solutions.

Due to the enormous threat of protactinium to the environment and human health, its disposal and chemistry have long been important topics in nuclear science. [PaO(H₂O)₆]3+ is proposed as the predominant species in hydrous and acidic solutions, but little is known about its formation mechanism. In this study, density functional theory (DFT) calculations demonstrate a water coordination-proton transfer-water dissociation mechanism for the formation of PaO3+ in hydrous solutions. First, Pa(V) ion preferentially forms hydrated complexes with a coordination number of 10. Through hydrogen bonding, water molecules in the second coordination sphere easily capture two protons on the same coordinated H₂O ligand to form [PaO(H₂O)₉]3+. Water dissociation then occurs to generate the final [PaO(H₂O)₆]3+, which is the thermodynamic product of Pa(V) in hydrous solutions.