Abstract

A report of Dirac molecular orbital calculations performed on the octahedral paramagnetic Re6S8Cl63- cluster ion was presented. The manifold of closely spaced unoccupied energy levels were found to be localized on the octahedral core and the cluster highest molecular orbital is largely centered on the terminal chloride ligand. The electronic features of the excited states were found to be similar to the intensely luminescent Re6S8Cl64- cluster ions. An isotropic Zeeman tensor predicted in the calculations was in good agreement with the single crystal solid state cluster electron paramagnetic resonance (EPR) experiments.