Dirac molecular orbital calculations on the octahedral rhenium clusters Re6S8X4-6 (where X=Cl, Br, I) are reported. The calculated relativistic molecular orbitals indicate that the manifold of closely spaced unoccupied energy levels are mainly localized on the octahedral rhenium core with some contributions from the μ3-S ligands, while all the cluster highest occupied molecular orbitals are largely centered on the terminal halide ligands. All three hexanuclear rhenium cluster ions have singlet ground state (spanning the Γ-6 symmetry) and are therefore diamagnetic. They have the same ground state and excited state features as the intensely luminescent W6Cl2-14 cluster ion. The calculated charge distributions indicate that these clusters could be formulated as: Re-0.216S-0.168Cl -0.246, Re-0.236S-0.178Br -0.216 and Re-0.266S-0.268I -0.126, respectively.
|Number of pages||4|
|Journal||Journal of Chemical Physics|
|Publication status||Published - 1 Feb 1999|
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry