高等学校化学学报

高等学校化学学报 ›› 1998, Vol. 19 ›› Issue (10): 1659.

• 论文 • 上一篇    下一篇

簇合物Mo2X4(X＝S,O)电子结构和光谱性质的Ab Initio研究

章永凡, 吴立明, 李俊篯, 黄尊行, 胡建明, 周立新   

  1. 福州大学化学系、结构化学国家重点实验室, 福州, 350002
  • 收稿日期:1997-07-22 出版日期:1998-10-24 发布日期:1998-10-24
  • 通讯作者: 李俊
  • 作者简介:章永凡,男,24岁,硕士研究生.
  • 基金资助:

    国家自然科学基金(批准号:29673010)和结构化学国家重点实验室基金资助课题.

Ab Initio Study on the Electronic Structures and the Spectra Properties of the Mo2X4(X＝S,O)Clusters

ZHANG Yong-Fan, WU Li-Ming, LI Jun-Qian, HUANG Zun-Xing, HU Jia-Ming, ZHOU Li-Xin   

  1. Department of Chemistry, State Key Laboratory of Structure Chemistry, Fuzhou University, Fuzhou, 350002
  • Received:1997-07-22 Online:1998-10-24 Published:1998-10-24

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摘要： 在abinitio水平上对含cis/trans-MO2S4核和含Mo2O4核簇合物的电子结构进行了研究.对钼原子选取和构造了一组适合于含Mo-Mo金属键的双核钼簇合物从头算的(4s4p2d)基组,利用该基组并结合自然键轨道(NBO)方法,对含上述簇胳的3个簇合物的电子结构进行了研究,并与相应的钨簇合物进行了比较.

关键词: 双核钼-硫簇合物, 红外振动光谱, 电子光谱, 化学键

Abstract: Using ab initio method, the electronic structures of the clusters containing the cis (Ⅰ)/ trans (Ⅰ') Mo2S4 and Mo 2O4(Ⅱ) core have been studied. The (4s4p2d) pseudopotential basis set of Mo atom has been chosen for the calculations of the dinuclear molybdenum clusters by optimizing the geometry of cluster(Ⅰ). The chemical bondings of three clusters are discussed by using the natural bond orbital(NBO) method and comparing with the similar dinuclear tungsten clusters. The IRvibration frequencies of three clusters have been calculated, the main absorption bands are assigned and compared with each other. The electronic spectra have been calculated using the CISmethod, it is shown that the lowest excited states of three clusters are the result from two transitions, σ(Mo-Mo)→ π (Mo-Xt*) (X=S,O) and σ(Mo-Mo)→ σ(Mo-Mo*), and the contribution of the former are greater.

Key words: Dinuclear molybdenum clusters, IR spectra, Electronic spectra, Chemical bond

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