Excited states of polonium(IV): electron correlation and spin-orbit coupling in the Po4+ free ion and in the bare and solvated [PoCl5]- and [PoCl6]2- complexes.

Abstract

Polonium (Po, Z = 84) is a main-block element with poorly known physico-chemical properties. Not much information has been firmly acquired since its discovery by Marie and Pierre Curie in 1898, especially regarding its speciation in aqueous solution and spectroscopy. In this work, we revisit the absorption properties of two complexes, [PoCl5]- and [PoCl6]2-, using quantum mechanical calculations. These complexes have the potential to exhibit a maximum absorption at 418 nm in HCl medium (for concentrations of 0.5 mol L-1 and above). Initially, we examine the electronic spectra of the Po4+ free ion and of its isoelectronic analogue, Bi3+, in the spin-orbit configuration interaction (SOCI) framework. Our findings demonstrate that the SOCI matrix should be dressed with correlated electronic energies and that the quality of the spectra is largely improved by decontracting the reference states at the complete active space plus singles (CAS + S) level. Subsequently, we investigate the absorption properties of the [PoCl5]- and [PoCl6]2- complexes in two stages. Firstly, we perform methodological tests at the MP2/def2-TZVP gas phase geometries, indicating that the decontraction of the reference states can be skipped without compromising the accuracy significantly. Secondly, we study the solution absorption properties by means of single-point calculations performed at the solvated geometries, obtained by an implicit solvation treatment or a combination of implicit and explicit solvation. Our results highlight the importance of saturating the first coordination sphere of the PoIV ion to obtain a qualitatively correct picture. Finally, we conclude that the known-for-decades 418 nm peak could be attributed to a mixture of both the [PoCl5(H2O)]- and [PoCl6]2- complexes. This finding not only aligns with the behaviour of the analogous BiIII ion under similar conditions but also potentially provides an explanation for previous discrepancies in the literature.