On the Electronic Structure of Distorted Cubic Rhodium Cluster Complexes Containing Bridging Germanium or Phosphorus Ligands

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• 作者：Bachir Zouchoune ; Jean-Yves Saillard and Jean-Fran?ois Halet
• 关键词：Electronic structure ; DFT calculations ; Transition metal clusters
• 刊名：Journal of Cluster Science
• 出版年：2007
• 出版时间：September, 2007
• 年：2007
• 卷：18
• 期：3
• 页码：720-728
• 全文大小：433 KB
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Catalysis
  Inorganic Chemistry
  Physical Chemistry
  
• 出版者：Springer Netherlands
• ISSN：1572-8862

文摘

DFT calculations show that the optimal metal valence electron (MVE) count of omnicapped cubic rhodium clusters containing more than eight terminal ligands, is 114. For such a count, a closed-shell configuration is computed with a substantial HOMO-LUMO gap. The presence of more than eight terminal ligands in the clusters favors highly distorted cubic architectures with capping ligands asymmetrically bound to the distorted metallic square faces. Removal of terminal ligands leads to the replacement of bonding M–L electron pairs by nonbonding electron pairs localized on the metal atoms, giving rise to unchanged MVE count.