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 orbita ls density functional (LCGTO-DF) method. The optimized geometries compare w ell with available experimental structures, especially with respect to the metal-metal bond distances Pt-Pt and Pt-Fe. The trend of these calculated b ond distances within the series is consistent with experiment and suggests a Pt-Pt anti-bonding character of the highest occupied molecular orbital (H OMO). Further insight into the clusters electronic structure has been gaine d from calculated binding energies, ionization potentials and electron affi nities. The electronic structure of the mono-anion suggests that this clust er may serve as good candidate for a recently suggested novel type of molec ular magnetism. (C) 1999 Elsevier Science S.A. All rights reserved.