Citation: CAO Fei, TAN Kai, LIN Meng-Hai. Geometric and Electronic Structures of Hexanuclear Binary Ta/Rh Mixed Clusters[J]. Acta Physico-Chimica Sinica, ;2010, 26(11): 3061-3066. doi: 10.3866/PKU.WHXB20101112 shu

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

CAO Fei ^1,2, ,
TAN Kai ² ,
LIN Meng-Hai ²

1.
1. College of Chemistry and Chemical Engineering, Jiujiang University, Jiujiang 332005, Jiangxi Province, P. R. China;
2. Departmental of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China

Received Date: 13 June 2010
Available Online: 17 September 2010
Fund Project: 国家自然科学基金(20873107, 20373053)资助项目 (20873107, 20373053)

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.
- Density functional theory,
- Transition-metal cluster,
- Metal bond,
- Tantalum,
- Rhodium
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