QTAIM Analysis in the Context of Quasirelativistic Quantum Calculations

Computational chemistry currently lacks ad hoc tools for probing the nature of chemical bonds in heavy and superheavy-atom systems where the consideration of spinorbit coupling (SOC) effects is mandatory. We report an implementation of the Quantum Theory of Atoms-In-Molecules in the framework of two-component relativistic calculations. Used in conjunction with the topological analysis of the Electron Localization Function, we show for astatine (At) species that SOC significantly lowers At electronegativity and boosts its propensity to make charge-shift bonds. Relativistic spin-dependent effects are furthermore able to change some bonds from mainly covalent to charge-shift type. The implication of the disclosed features regarding the rationalization of the labeling protocols used in nuclear medicine for At-211 radioisotope nicely illustrates the potential of the introduced methodology for investigating the chemistry of (super)heavy elements.