Three-site transition-metal clusters: Going from localized electrons to molecular orbitals

Abstract

Investigation of the recently synthesized series of isostructural compounds Ba4NbTM3O12 (TM=Mn, Rh, and Ir) with transition-metal trimers in a face-sharing geometry makes it possible to examine a tendency to the molecular orbitals (MO) formation going from 3d to 5d transition metal ions. Our ab initio calculations of electronic and magnetic properties describe the experimental findings and demonstrate gradual transition from the picture of localized electrons for Mn to the MO picture for Rh and especially for Ir. We also show that the often used criterion, according to which the metal-metal distance in a compound shorter than in a respective metal always gives MO, may break down in some cases. © 2020 American Physical Society.