Coordination and thermodynamic properties of aqueous protactinium(V) by first-principle calculations

TL;DR

This study uses first-principle calculations combined with experimental data to investigate the complexation behavior and thermodynamic properties of aqueous protactinium(V), highlighting the importance of coordination saturation and hydroxyl group retention.

Contribution

It demonstrates the necessity of saturating the coordination sphere and maintaining hydroxyl groups in modeling protactinium(V) complexes, advancing theoretical understanding of its solution chemistry.

Findings

Coordination saturation is essential for accurate equilibrium constants.

Hydroxyl groups are retained in 1:1 complexes but withdrawn in higher ligand coordination.

The work provides a methodological framework for future theoretical studies of protactinium chemistry.

Abstract

Protactinium ($Z$ = 91) is a very rare actinide with peculiar physico-chemical properties. Indeed, although one may naively think that it behaves similarly to either thorium or uranium by its position in the periodic table, it may in fact follow its own rules. Because of the quite small energy gap between its valence shells (in particular the 5$f$ and 6$d$ ones) and also the strong influence of relativistic effects on its properties, it is actually a challenging element for theoretical chemists. In this article, we combine experimental information, chemical arguments and standard first-principle calculations, complemented by implicit and explicit solvation, to revisit the stepwise complexation of aqueous protactinium(V) with sulfate and oxalate dianionic ligands (SO$_4$$^{2-}$ and C$_2$O$_4$$^{2-}$, respectively). From a methodological viewpoint, we notably conclude that it is necessary to at least saturate the coordination sphere of protactinium(V) to reach converged equilibrium constant values. Furthermore, in the case of single complexations (i.e. with one sulfate or oxalate ligand bound in the bidentate fashion), we show that it is necessary to maintain the coordination of one hydroxyl group, present in the supposed [PaO(OH)]$^{2+}$ precursor, to obtain coherent complexation constants. Therefore, we predict that this hydroxyl group is maintained in the formation of 1:1 complexes while we confirm that it is withdrawn when coordinating three sulfate or oxalate ligands. Finally, we stress that this work is a first step toward the future use of theoretical predictions to elucidate the enigmatic chemistry of protactinium in solution.