title: QTAIM Analysis in the Context of Quasirelativistic Quantum Calculations.
abstract: Computational chemistry currently lacks ad hoc tools for probing the nature of chemical bonds in heavy and superheavy-atom systems where the consideration of spin-orbit 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 (211)At radioisotope nicely illustrates the potential of the introduced methodology for investigating the chemistry of (super)heavy elements.
authors.affiliation: Laboratoire de Chimie Théorique, Sorbonne Universités, UPMC Université Paris 06, UMR 7616 , F-75005 Paris, France.|Laboratoire de Chimie Théorique, CNRS UMR 7616 , F-75005 Paris, France.
authors.forename: Julien
authors.initials: J
authors.lastname: Pilmé
authors.affiliation: CEISAM, UMR CNRS 6230, Université de Nantes , 2 Rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3, France.
authors.forename: Eric
authors.initials: E
authors.lastname: Renault
authors.affiliation: CEISAM, UMR CNRS 6230, Université de Nantes , 2 Rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3, France.
authors.forename: Fadel
authors.initials: F
authors.lastname: Bassal
authors.affiliation: Laboratoire de Chimie Théorique, Sorbonne Universités, UPMC Université Paris 06, UMR 7616 , F-75005 Paris, France.|Laboratoire de Chimie Théorique, CNRS UMR 7616 , F-75005 Paris, France.
authors.forename: Mohamed
authors.initials: M
authors.lastname: Amaouch
authors.affiliation: SUBATECH, UMR CNRS 6457, IN2P3/EMN Nantes/Université de Nantes , 4 rue A. Kastler, BP 20722, 44307 Nantes Cedex 3, France.
authors.forename: Gilles
authors.initials: G
authors.lastname: Montavon
authors.affiliation: CEISAM, UMR CNRS 6230, Université de Nantes , 2 Rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3, France.
authors.forename: Nicolas
authors.initials: N
authors.lastname: Galland