Density Functional Theory Studies on the Electronic Properties of Dilacunary gamma-Keggin Polyoxometalate Anions

作者：Zhang Di; Dou Zhuo; Zhang Ting; Yan Li-Kai^*; Su Zhong-Min

来源：Chemical Journal of Chinese Universities, 2011, 32(11): 2613-2617.

• Dilacunary gamma-Keggin polyanion
• Electronic property
• Redox property
• Density functional theory

The geometrical structures and electronic properties of dilacunary gamma-Keggin polyanions [gamma-Xn+ (WO36)-O-10]((12-n)-) (X = Al-III, Si-IV, P-V, S-VI, Ga-III, Ge-IV, As-V, Se-VI) were investigated via density functional theory(DFT) methods. The results show that the bond lengths between central tetrahedral oxygen atom O-a and central heteroatom X, as well as tungsten atom depend on the central heteroatom X. However, the sizes of XO4 are independent with the central heteroatom. The highest occupied molecular orbital(HOMO) of [gamma-Xn+ (WO36)-O-10]((12-n)-) mainly concentrates on the bridge oxygen atoms. Except for [gamma-SeW10O36](6-), the lowest unoccupied molecular orbital(LUMO) of polyanion is from d orbitals of tungsten atoms. The energies of HOMO and LUMO of [gamma-Xn+ (WO36)-O-10]((12-n)-) depend on the central heteroatom X. The LUMO energy decreases with the increasing of the atomic numbers, and the central atoms are in the same row in periodic table.

• 出版日期2011-11-10
• 单位东北师范大学