高等学校化学学报

高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (4): 652.

• 研究论文 • 上一篇    下一篇

Dawson结构杂多阴离子(P2M18O62)6-(M=Mo,W)的电子结构和催化性质的理论研究

肖慎修, 杨胜勇, 陈天朗, 王荣顺   

  1. 四川大学化学学院, 成都 610064
  • 收稿日期:2000-11-20 出版日期:2002-04-24 发布日期:2002-04-24
  • 通讯作者: 肖慎修(1936年出生),女,教授,主要从事应用量子化学研究.E-mail:nic3002@scu.edu.cn E-mail:nic3002@scu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:29643002)资助.

Studies on the Relationship Between Electronic Structuresand Catalytic Properties of Dawson HPA Anion

XIAO Shen-Xiu, YANG Sheng-Yong, CHEN Tian-Lang, WANG Rong-Shun   

  1. Institute of Chemistry, Sichuan University, Chengdu 610064, China
  • Received:2000-11-20 Online:2002-04-24 Published:2002-04-24

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摘要： 用第一原理密度泛函理论的离散变分方法(DFT-DVM)计算典型的Dawson结构杂多阴离子(P2M18O62)6-(M=Mo,W)的电子结构,比较两者之间的差异。结果表明,Dawson结构中极位和赤道位的原子有不同的化学行为,还原电子将主要进入赤道位的金属原子。(P2Mo8O62)6-的反应活性中心主要是配位金属原子Mo、极位桥氧Opb、赤道位端氧Oet和赤道位中心氧Oei;(P2W18O62)6-的反应活性中心主要是配位金属原子W、极位桥氧Opb、赤道位端氧Oet.(P2Mo8O62)6-的氧化性强于(P2W18O62)6-,而酸性则与此相反。这与Keggin结构(PM12O40)3-杂多阴离子的情况相同。

关键词: Dawson结构杂多阴离子, (P2Mo18O62)6-, (P2W18O62)6-, 电子结构, 密度泛函理论, 离散变分方法

Abstract: The electronic structures of Dawson HPA anion(P2M18O62)6-(M=Mo,W) have been calculat-ed by the discrete variational method coupled with the first principle density functional theory (DFT-DVM).The results show that the difference of the chemical properties of polar and equator sites exists.The reduction electrons will be introduced mainly into equatorial metal atoms.The active centers of(P2Mo18O62)6- are Mo, Opb, Oet, Oei and that of (P2W18O62)6- are W, Opb, Oet The redox effect of(P2Mo18O62)6- is stronger than that of (P2W18O62)6-, but their acidities are quite the opposite, which areall the same as those of (PM12O40)3- (M=Mo, W).

Key words: Dawson HPA anion, (P2Mo18O62)6-, (P2W18O62)6-, Elecrtronic structure, Density function theory(DFT), Discrete variational method(DVM)

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