化学学报 ›› 1995, Vol. 53 ›› Issue (7): 695-701. 上一篇    下一篇

研究论文

双核簇合物M~2S~2(μ-S)~2(dtp)~2(M=Mo, W)的电子结构及元件组装活性的abinitio研究

陈瑞芝;李隽;刘春万;蔡新华;孟令鹏;郑世钧   

  1. 河北师范学院化学系计算量子化学研究室;中国科学院福建物质结构研究所;河北师范学院化学系计算量子化学研究室
  • 出版日期:1995-07-15 发布日期:1995-07-15

Ab initio studies on electronic structures and unit construction reactivity of dinuclear complexes M~2S~2(μ-S)~2(dtp)~2(M=Mo, W)

CHEN RUIZHI;LI JUAN;LIU CHUNWAN;CAI XINHUA;MENG LINGPENG;ZHENG SHIJUN   

  • Online:1995-07-15 Published:1995-07-15

本文对双核簇合物M~2S~2(μ-S)~2(dtp)~2(M=Mo, W)及其簇芯碎片M~2S~4^2^+进行了相对论赝势从头算和Boys定域化分子轨道计算, 根据所计算的正则分子轨道(CMO)和定域分子轨道(LMO)以及Mulliken布居分析, 探讨了作为簇元元件的M~2S~4(dtp)~2的成键性质和电子结构, 利用广义微扰理论, 定性分析了M~2S~4^2^+型簇合物的元件组装活性位和活性区, 研究了它们发生[2+1]=3和[2+2]=4型元件组装的成簇机理。

关键词: 活性, 从头计算法, 组装, 分子轨道方法, 定域化, 元件, 双核簇合物, 成簇机理

The electronic structure calculations have been carried out on two binuclear complexes Mo~2S~2(μ-S)~2(dtp)~2 (1), W~2S~2(μ-S)~2(dtp)~2 (2) and their core fragments Mo~2S~4^2^+ (3), W~2S~4^2^+ (4). The calculations were accomplished by using an ab initio quantum chemical method with relativistic effective core potentials. By the analysis of the calculated canonical molecular orbitals and localized molcular orbitals as well as the Mulliken populations, the bonding and electronic characteristics of these complexes have been studied. By virtue of the Generalized Purtubation theory, there activities and mechanism of M~2S~4^2^+ complexes in forming the Cubane-like clusters via [2+2] fasion and the incomplete Cubane-type clusters via [2+1] fashion have been discussed. It is found that there exist three "Reactive Sites" and three "Reactive Regions" with higher electronic densities.

Key words: ACTIVITY, AB INITIO CALCULATION, ASSEMBLING, MOLECULAR ORBITAL METHOD, LOCALIZATION, ELEMENTS

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