Relativistic density functional study on the bimetallic cluster [Pt₃Fe₃(CO)₁₅]^n- (n=0, 1, 2)

The bimetallic cluster [Pt₃Fe₃(CO)₁₅]^n- (n=0, 1, 2) has been studied with the scalar-relativistic linear combination of the Gaussian-type orbitals density functional (LCGTO-DF) method. The optimized geometries compare well with available experimental structures, especially with respect to the metal-metal bond distances Pt-Pt and Pt-Fe. The trend of these calculated bond distances within the series is consistent with experiment and suggests a Pt-Pt anti-bonding character of the highest occupied molecular orbital (HOMO). Further insight into the clusters electronic structure has been gained from calculated binding energies, ionization potentials and electron affinities. The electronic structure of the mono-anion suggests that this cluster may serve as good candidate for a recently suggested novel type of molecular magnetism.