高等学校化学学报

高等学校化学学报 ›› 1994, Vol. 15 ›› Issue (10): 1534.

• 论文 • 上一篇    下一篇

1Σ+Ni─CO分子簇的从头算研究

徐昕, 王南钦, 吕鑫, 张乾二   

  1. 厦门大学化学系, 固体表面物理化学国家重点实验室, 厦门, 361005
  • 收稿日期:1993-12-14 修回日期:1994-06-28 出版日期:1994-10-24 发布日期:1994-10-24
  • 通讯作者: 徐听,男,30岁,副教授.
  • 作者简介:徐听,男,30岁,副教授.
  • 基金资助:

    国家自然科学基金

Ab Initio Calculations of 1Σ+ Ni─CO Molecular Cluster

XU Xin, WANG Nan-Qin, LU Xin, ZHANG Qian-Er   

  1. State Key Lab.of Phys.Chem.on Solid Surfaces, Dept of Chem.Xiamen Univ.Xiamen, 361005
  • Received:1993-12-14 Revised:1994-06-28 Online:1994-10-24 Published:1994-10-24

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摘要： 采用UHF及UMP2方法,对1Σ+Ni─CO分子簇的成键机制进行了从头算研究。计算表明,在σ空间,Ni1S(d10)导出态的主要成键特征是CO 5σ→Ni4s的授键作用；而Ni1D(d9s1)导出态的主要特征是4spσ极化。在1Σ+Ni─CO分子簇中总的成键机制是：d10导出态中π反馈作用大于σ授键作用；而d9s1导出态中σ授键作用强于π反馈作用。由于接受配键机制一定伴随着轨道之间的重叠,因而为了给出合理的M─L作用分析,进行补偿计算是重要的。

关键词: 1&Sigma, +Ni─CO簇, 从头算, 补偿计算

Abstract: UHFand UMP2 are employed to investigate the bonding mechanism of 1Σ+Ni-COmolecular cluster.The calculation results show that, in 1Σ+Ni─CO σ subspace, CO5σ→Ni4sσ donation dominates in Ni1 S(d10 )derived state, while 4spσpolarization dominates in Ni1D(d9s1)derived state.The π backdonation is greater than σ donation in d10 derived state, while σ donation is more important than π backdonation in d9s1 derived state, The calculation results demonstrate that it is important to perform a counterpoise calculation because there must exist an orbital overlapping in a donor-acceptor bonding mechanism.

Key words: 1Σ+Ni─CO molecular cluster, Ab initio, Counterpoise calculation

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