Quantum chemical topology at the spin-orbit configuration interaction level: Application to astatine compounds.

Abstract

We report a methodology that allows the investigation of the consequences of the spin-orbit coupling by means of the QTAIM and ELF topological analyses performed on top of relativistic and multiconfigurational wave functions. In practice, it relies on the "state-specific" natural orbitals (NOs; expressed in a Cartesian Gaussian-type orbital basis) and their occupation numbers (ONs) for the quantum state of interest, arising from a spin-orbit configuration interaction calculation. The ground states of astatine diatomic molecules (AtX with X = AtF) and trihalide anions (IAtI- , BrAtBr- , and IAtBr- ) are studied, at exact two-component relativistic coupled cluster geometries, revealing unusual topological properties as well as a significant role of the spin-orbit coupling on these. In essence, the presented methodology can also be applied to the ground and/or excited states of any compound, with controlled validity up to including elements with active 5d, 6p, and/or 5f shells, and potential limitations starting with active 6d, 7p, and/or 6f shells bearing strong spin-orbit couplings.