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

Abstract

A recently synthesised series of isostructural compounds Ba${}_4$NbTM${}_3$O${}_{12}$ (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.

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Cited by in corpus (5)

• Magnetic molecular orbitals in MnSi
• Clusterization transition between cluster Mott insulators on a breathing Kagomé lattice
• Can the highly symmetric SU(4) spin-orbital model be realized in alpha-ZrCl3?
• Static magnetic and ESR spectroscopic properties of the dimer-chain antiferromagnet BiCoPO${}_5$
• Quasimolecular electronic structure of the trimer iridate Ba${}_4$NbIr${}_3$O${}_{12}$