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Polonium (Z = 84) is one of the rarest elements on Earth. More than a centuryafter its discovery, its chemistry remains poorly known and even basicquestions are not yet satisfactorily addressed. In this work, we perform asystematic study of the geometries, interactions energies and bonding in basicpolonium(IV) species, namely the hydrated [Po(H$_2$O)$_n$]$^{4+}$ andchlorinated [PoCl$_n$]$^{4-n}$ complexes by means of gas-phase electronicstructure calculations. We show that while up to nine water molecules can fitin the first coordination sphere of the polonium(IV) ion, its coordinationsphere can already be filled with eight chloride ligands. Capitalising onprevious theoretical studies, a focused methodological study based oninteraction energies and bond distances allows us to validate the MP2/def2-TZVP level of theory for future ground-state studies. After discussingsimilarities and differences between complexes with the same number of ligands,we perform topological analyses of the MP2 electron densities in the quantumtheory of atoms in molecules (QTAIM) fashion. While the water complexes displaytypical signatures of closed-shell interactions, we reveal large Po-Cldelocalisation indices, especially in the hypothetical [PoCl]$^{3+}$ complex.This "enhanced" covalency opens the way for a significant spin-orbit coupling(SOC) effect on the corresponding bond distance, which has been studied by twoindependent approaches (i.e. one a priori and one a posteriori). We finallyconclude by stressing that while the SOC may not affect much the geometries ofhigh-coordinated polonium(IV) complexes, it should definitely not be neglectedin the case of low-coordinated ones.

Geometries, interaction energies and bonding in [Po(H$_2$O)$_n$]$^{4+}$ and [PoCl$_n$]$^{4-n}$ complexes