Stability of the Protactinium(V) Mono-Oxo Cation Probed by First-Principle Calculations.

ABSTRACT

This study explores the distinctive behavior of protactinium (Z=91) within the actinide series. In contrast to neighboring elements like uranium or plutonium, protactinium in the pentavalent state diverges by not forming the typical dioxo protactinyl moiety PaO2 + in aqueous phase. Instead, it manifests as a monooxo PaO3+ cation or a Pa5+ . Employing first-principle calculations with implicit and explicit solvation, we investigate two stoichiometrically equivalent neutral complexes PaO(OH)2 (X)(H2 O) and Pa(OH)4 (X), where X represents various monodentate and bidentate ligands. Calculating the Gibbs free energy for the reaction PaO(OH)2 (X)(H2 O)→Pa(OH)4 (X), we find that the PaO(OH)2 (X)(H2 O) complex is stabilized with Cl- , Br- , I- , NCS- , NO3 - , and SO4 2- ligands, while it is not favored with OH- , F- , and C2 O4 2- ligands. Quantum Theory of Atoms in Molecules (QTAIM) and Natural Bond Orbital (NBO) methods reveal the Pa mono-oxo bond as a triple bond, with significant contributions from the 5f and 6d shells. Covalency of the Pa mono-oxo bond increases with certain ligands, such as Cl- , Br- , I- , NCS- , and NO3 - . These findings elucidate protactinium's unique chemical attributes and provide insights into the conditions supporting the stability of relevant complexes.