|
 |
electronic structure aquaoxomolybdenum aquathioxomolybdenum cation; oxoaquamolybdenum cation electronic structure; thioxoaquamolybdenum cation electronic structure; molybdenum aquaoxo aquathioxo cation electronic structure; HOMO aquaoxomolybdenum aquathioxomolybdenum cation; LUMO aquaoxomolybdenum aquathioxomolybdenum cation; MO aquaoxomolybdenum aquathioxomolybdenum cation; XPS aquaoxomolybdenum aquathioxomolybdenum cation; spectra electronic aquaoxomolybdenum aquathioxomolybdenum cation; acetylene reactivity aquaoxomolybdenum aquathioxomolybdenum cation; mol structure aquaoxomolybdenum aquathioxomolybdenum cation
Electronic structures of two incomplete cubane-type clusters [Mo3X4(H2O)9]4+ (X = O, S) have been calcd. by the discrete-variational (DV)-Xα method. The calcns. explain the exptl. results of valence-band x-ray photoelectron spectra, electronic spectra, and reactivity difference toward acetylene. The net charge of Mo in [Mo3S4(H2O)9]4+ (S) is more neg. than that of Mo in [Mo3O4(H2O)9]4+ (O); the bridging sulfur atoms are the main neg. charge-source for the molybdenum atoms in the cluster S. As for S, levels of HOMO (45e) and LUMO (46e) consist mainly of Mo 4d and μ-S 3p AOs, and contribution of μ3-S 3p to the orbitals is not large. The existence of Mo-Mo, Mo-μ-S, and Mo-μ3-S bonds is clear from the contour maps of the orbitals. As for O, levels of HOMO (40e) and LUMO (41e) consist mainly of Mo 4d and μ-O 2p AOs. Contribution of μ3-O 2p to the orbitals is not large except in the orbital 30a1. The existence of Mo-Mo, Mo-μ-O, and Mo-μ3-O bonds also is appreciable from the contour maps of the orbitals.
Discrete variational (DV)-Xα calculations of incomplete cubane-type molybdenum clusters [Mo3X4(H2O)9]4+ (X = O, S)
Research papers (academic journals)
