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

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

六聚同多酸阴离子M₆O₁₉^n-（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. 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, M₆O₁₉^n- (M=Mo, W, n=2; M=Nb, Ta, n=8)

LIU Shi-Xi^1,2, YUE Bin¹, TAN De-Jun¹, ZHAO Dong¹, XU Jing-Yu¹, JIN Song-Lin¹, FAN Kang-Nian¹, HE He-Yong¹

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

Abstract

The electronic structures, IR frequencies, HOMO-LUMO population of four hexaoxoanions (M₆O₁₉^n-, 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: Mo₆O₁₉^2- and W 6O₁₉^2- which are electron acceptors, and Nb₆O₁₉^8- and Ta₆O₁₉^8- which are electron donors.LUMO orbitals of Mo₆O₁₉2- and W₆O₁₉^2- consist of p orbitals of bridge oxygen atom and inner d orbitals of metal atom, whereas Nb 6O 8- 19 and Ta₆O₁₉^8- 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

Cite this article

LIU Shi-Xi, YUE Bin, TAN De-Jun, ZHAO Dong, XU Jing-Yu, JIN Song-Lin, FAN Kang-Nian, HE He-Yong. A DFT Study of the Electronic Structures and Chemical Properties of Hexaoxoanions, M₆O₁₉^n- (M=Mo, W, n=2; M=Nb, Ta, n=8)[J]. Acta Chimica Sinica, 2004, 62(17): 1579-1584.

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六聚同多酸阴离子M₆O₁₉^n-（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

A DFT Study of the Electronic Structures and Chemical Properties of Hexaoxoanions, M₆O₁₉^n- (M=Mo, W, n=2; M=Nb, Ta, n=8)

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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