Free electron model in cluster structure theory.: Electronic structures of [Mo6S8(CN)6]6-, [Mo6Se8(CN)6]6-, [Re6S8(CN)6]4-, and Rh6(CO)16 clusters

The results of quantum chemical calculations of the electronic structure and geometry of octahedral clusters [Mo6S8(CN)(6)](6-), [Mo6Se8(CN)(6)](6-), [Re(6)Sg(CN)(6)](4-), and Rh-6(CO)(16) by the ab initio SCF (RHF) and DFT (B3LYP) methods with various basis sets are presented. The electronic states of the clusters under study in ideal spherically symmetric potential were classified in the orbital quantum number l (1s, 1p, 1d, 1f, 1g, 1h, 1i), l = 0-6. In real crystal field with O-h symmetry these states are split. The calculated new electronic states were matched to the irreducible representations of the point symmetry group O-h. The polarizabilities of the compounds considered are 55-65 angstrom(3). A new model for the electronic structure of octahedral clusters containing M-6 groups was proposed. The model is based on the idea of free electrons moving in spherically symmetric potential field.