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Discrete Variational (DV)-Xα Calculations of Incomplete Cubane-Type Molybdenum Clusters [Mo3X4(H2O)9]4+ (X= O,S)1

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Abstract

Electronic structures of two incomplete cubane-type clusters [Mo3X4(H2O)9]4+ (X =O, S) have been calculated by the discrete-variational (DV)-Xα method. The calculations explain the experimental 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 negative than that of Mo in [MO3O4H2O)4+] (O), and the bridging sulfur atoms are the main negative 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 andμ-S 3p atomic orbitals, and contribution ofμ 3-S 3p to the orbitals is not large. The existence of Mo-Mo, Mo-μ-S, and Mo-μ 3-S bounds is clear from the contour maps of the orbitals. As for O levels of HOMO (40e) and LUMO (41c) consist mainly of Mo 4d andμ-O 2p atomic orbitals. Contribution ofμ 3-O 2p to the orbitals is not large except in the orbital 30a1,. The existence of Mo-Mo, Mo-μ-O, and MO-μ 3-O bonds also is appreciable from the contour maps of the orbitals.

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Authors and Affiliations

  1. Department of Chemistry, Okayama University of Science, 1-1 Ridai-cho, 700, Okayama, Japan

    Genta Sakane & Takashi Shibahara

  2. Department of Materials Science and Engineering, Kyoto University, Yoshida-honmachi, 606-01, Sakyo-ku, Kyoto, Japan

    Hirohiko Adachi

Authors
  1. Genta Sakane
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  2. Takashi Shibahara
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  3. Hirohiko Adachi
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Dedicated to Professor Jiaxi Lu on the occasion of his 80th birthday.

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Sakane, G., Shibahara, T. & Adachi, H. Discrete Variational (DV)-Xα Calculations of Incomplete Cubane-Type Molybdenum Clusters [Mo3X4(H2O)9]4+ (X= O,S)1 . J Clust Sci 6, 503–521 (1995). https://doi.org/10.1007/BF01165770

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