Acta Chimica Sinica ›› 2004, Vol. 62 ›› Issue (17): 1579-1584.     Next Articles

六聚同多酸阴离子M6O19n-(M=Mo,W,n=2;M=Nb,Ta,n=8)电子结构和化学性质的密度泛函理论研究

刘世熙1,2, 岳斌1, 谭德军1, 赵栋1, 许静玉1, 金松林1, 范康年1, 贺鹤勇1   

  1. 1. 复旦大学化学系, 上海市分子催化和功能材料重点实验室, 上海, 200433;
    2. 云南大学化学系, 云南大学现代生物学研究中心, 昆明, 650091
  • 投稿日期:2004-01-12 修回日期:2004-04-05 发布日期:2014-02-17
  • 通讯作者: yuebin@fudan.edu.cn;heyonghe@fudan.edu.cn
  • 作者简介:岳斌,E-mail:yuebin@fudan.edu.cn;贺鹤勇,E-mail:heyonghe@fudan.edu.cn;Fax:85-21-65642978
  • 基金资助:
    国家自然科学基金(Nos.20371013,20005310)、上海市科学技术委员会重大基础研究项目(No.03DJ14004)和国家重点基础研究发展计划(No.2003CB615807)资助项目.

A DFT Study of the Electronic Structures and Chemical Properties of Hexaoxoanions, M6O19n- (M=Mo, W, n=2; M=Nb, Ta, n=8)

LIU Shi-Xi1,2, YUE Bin1, TAN De-Jun1, ZHAO Dong1, XU Jing-Yu1, JIN Song-Lin1, FAN Kang-Nian1, HE He-Yong1   

  1. 1. Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433;
    2. Department of Chemistry and Modern Biological Research Center, Yunnan University, Kunming 650091
  • Received:2004-01-12 Revised:2004-04-05 Published:2014-02-17

The electronic structures, IR frequencies, HOMO-LUMO population of four hexaoxoanions (M6O19n-, M=Mo and W, n=2; M=Nb and Ta, n=8) were studied by density functional theory method, B3LYP, at LanL2DZ level.According to the analysis of frontier orbitals and molecule electrostatic potential, these four anions can be classified into two types: Mo6O192- and W 6O192- which are electron acceptors, and Nb6O198- and Ta6O198- which are electron donors.LUMO orbitals of Mo6O192- and W6O192- consist of p orbitals of bridge oxygen atom and inner d orbitals of metal atom, whereas Nb 6O 8- 19 and Ta6O198- mainly consist of outer s and p orbitals of metal atom.Molecular electrostatic potential further exhibits the existing of electrophilic and nucleophilic sites in these anions.These results account for their different chemical properties such as the coordination ability and stability in aqueous solution.

Key words: hexaoxoanion, electronic structure, chemical property, frontier orbital, molecular electrostatic potential