Revisiting the role of octahedral symmetry in the interpretation of spectroscopic properties of [OsF6]2− and PtF6 complexes

Abstract

The electronic structure of [OsF₆]²⁻ and PtF₆ complexes was studied by means of CASSCF/NEVPT2 multiconfigurational calculations, including spin–orbital coupling, which is very relevant in the case of these metals. From these calculations, it is possible to establish that in the octahedral symmetry (O_h), the ground state is non-magnetic (J_eff = 0) because of the strong ligand field, and the interaction with paramagnetic excited states is almost negligible, resulting in a non-magnetic behavior, which is in agreement with the experimental evidence.