Calculated paramagnetic resonance parameters of the luminescent Re₆S₈Cl₆^3- cluster ion

A report of Dirac molecular orbital calculations performed on the octahedral paramagnetic Re₆S₈Cl₆^3- 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 Re₆S₈Cl₆^4- 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.