高等学校化学学报

高等学校化学学报 ›› 2003, Vol. 24 ›› Issue (10): 1862.

• 论文 • 上一篇    下一篇

Keggin结构多金属氧酸盐α-[SiW12O40]4-的从头算理论研究

郭元茹1, 潘清江2, 韦永德1, 李中华1, 周百斌1   

  1. 1. 哈尔滨工业大学应用化学系, 哈尔滨 150001;
    2. 黑龙江大学化学化工学院, 哈尔滨 150080
  • 收稿日期:2002-11-07 出版日期:2003-10-24 发布日期:2003-10-24
  • 通讯作者: 郭元茹(1975年出生),女,博士研究生,从事材料化学研究.E-mail:gyrhit@yahoo.com.cn E-mail:gyrhit@yahoo.com.cn
  • 基金资助:

    国家自然科学基金(批准号:29671009)资助

Ab initio Studies on Keggin Structure Polyoxometalate α-[SiW12O40]4-

GUO Yuan-Ru1, PAN Qing-Jiang2, WEI Yong-De1, LI Zhong-Hua1, ZHOU Bai-Bin1   

  1. 1. Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001, China;
    2. College of Chemistry and Chemical Engineering, Heilongjiang University, Harbin 150080, China
  • Received:2002-11-07 Online:2003-10-24 Published:2003-10-24

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摘要： 采用从头算Hartree-Fock方法对具有Keggin结构的多金属氧酸盐离子α-[SiW12O40]4-进行优化.以基态几何为基础,进行单激发组态相互作用(CIS)计算.结果表明,WO6单元形成扭曲的八面体,而SiO4部分仍具有准四面体结构;阴离子的4个三金属簇W3O13可容纳3～4个负电荷,从微观结构上揭示了杂多阴离子拥有大量负电荷仍能稳定的原因.

关键词: 从头算, Keggin结构, 多金属氧酸盐

Abstract: The polyoxometalate α-[SiW12O40]4-with the Keggin structure was fully optimized by the ab initio Hartree-Fock method.The optimized geometry parameters of the title compound agree with experimental values.Based on such calculations, the single excited configuration interaction (CIS) method was performed to calculate the excited states related to absorptions.The absorption maximum was calculated at 232nm by using the CIS method and assigned as Od→W and Oc→W charge transfer transition, comparable to the 260nm absorption of α-H4SiW12O40in the experiment.The calculations showed that the distortion of WO6unit can stabilize the whole molecule and the SiO4unit has the quasi-tetrahedral structure.The four W3O13units in the heteropolyacid can possess 3-4 negative charges, which theoretically reveals why the unit with more electrons in the anion is still stable.

Key words: Ab initio, Keggin structure, Polyoxometalate

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