六核钽铑二元混合簇合物的几何和电子结构

doi:10.3866/PKU.WHXB20101112

Abstract

Abstract:

Density functional theory (DFT) was employed to investigate the geometric and electronic properties of a series of hexanuclear binary Ta/Rh clusters. The results show that most of the stable structures of the Ta/Rh mixed clusters have low symmetry and belong to the C₁ or C_s point groups while the [Ta₂Rh₄Cl₄H₈(CN)₆]^4- clusters are highly symmetric (C_2h or C_4v). The energy gaps (△E_H-L) between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the mixed clusters are narrow and within 0.52-1.00 eV. A frontier orbital analysis of the mixed clusters clearly shows that the molecular orbitals are mainly composed of the d-orbitals of the skeleton metal atoms. When more rhodium atoms are substituted for tantalum atoms, the Ta—Rh bond has a greater influence on the stable structures of the mixed clusters and the influence of Ta—Ta bond decreases while the Rh—Rh bond has a non-bonding or anti-bonding nature.

Key words: Density functional theory, Transition-metal cluster, Metal bond, Tantalum, Rhodium

MSC2000:

O641

CAO Fei, TAN Kai, LIN Meng-Hai. Geometric and Electronic Structures of Hexanuclear Binary Ta/Rh Mixed Clusters[J].Acta Phys. -Chim. Sin., 2010, 26(11): 3061-3066.

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Geometric and Electronic Structures of Hexanuclear Binary Ta/Rh Mixed Clusters

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