高等学校化学学报

高等学校化学学报 ›› 2009, Vol. 30 ›› Issue (5): 1014.

• 研究论文 • 上一篇    下一篇

具有Lindqvist结构的[Mo6O19]2-化合物及其二钨取代物的电子性质和稳定性的理论研究

舒鑫1, 周欣1, 潘清江2, 李明霞2, 张红星1, 孙家锺1   

    1. 吉林大学理论化学研究所, 理论化学计算国家重点实验室, 长春 130023;
    2. 黑龙江大学化学化工与材料学院, 哈尔滨 150080
  • 收稿日期:2008-01-10 出版日期:2009-05-10 发布日期:2009-05-10
  • 通讯作者: 张红星, 男, 博士, 教授, 博士生导师, 主要从事量子化学计算研究, E-mail: zhanghx@mail.jlu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号: 20573042, 20703015)、黑龙江省自然科学基金(批准号: B200601)和黑龙江大学杰出青年基金(批准号: JC2006L2)资助.

Theoretical Study on Electronic Properties and Stability of [Mo6O19]2- and Tungsten Substituted Complexes Bearing Lindqvist Structure

SHU Xin1, ZHOU Xin1, PAN Qing-Jiang2, LI Ming-Xia2, ZHANG Hong-Xing1*, SUN Chia-Chung1   

    1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China;
    2. School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, China
  • Received:2008-01-10 Online:2009-05-10 Published:2009-05-10
  • Contact: ZHANG Hong-Xing, E-mail: zhanghx@mail.jlu.edu.cn

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摘要：

采用密度泛函理论研究了具有Lindqvist结构的[Mo6O19]2-及其两个钨原子取代化合物的电子性质和稳定性, 计算得到的几何数据和实验值符合得很好. 从Mulliken电荷分布、键能大小以及轨道性质的分析可以得出结论, 当两个钨原子在邻位取代钼原子时所得到的取代产物([4,5-W2Mo4O19]2-)比当两个钨原子在对位取代钼原子时所得到的产物([4,6-W2Mo4O19]2-)更稳定, 而[4,5-W2Mo4O19]2-的反应活性比[4,6-W2Mo4O19]2-的大.

关键词: 钼、钨多金属氧化物, 键能, 密度泛函理论

Abstract:

In order to understand the effects of substituted W atoms on the Mo Lindqvist-type complexes, the electronic properties and stability of the [Mo6O19]2- and its two W substituents were investigated via density functional theory(DFT) method at the BP86 functional level. The results are well consistent with the experimental values. According to the analysis of Mulliken population, bond energy and the frontier orbitals, we concluded that the [4,5-W2Mo4O19]2- is more stable than [4,6-W2Mo4O19]2-, however, the [4,5-W2Mo4O19]2- is more active than [4,6-W2Mo4O19]2-. Our calculations can provide the powerful theoretical support to the experimental investigation of the Lindqvist complexes.

Key words: Mo and W polyoxometalates, Bond energy, Density functional theory

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