Acta Phys. -Chim. Sin. ›› 2010, Vol. 26 ›› Issue (11): 3061-3066.doi: 10.3866/PKU.WHXB20101112

• QUANTUM CHEMISTRY AND COMPUTATION CHEMISTRY • Previous Articles     Next Articles

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

CAO Fei1,2, TAN Kai2, LIN Meng-Hai2   

  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:2010-06-13 Revised:2010-08-06 Published:2010-10-29
  • Contact: CAO Fei E-mail:jjyz2001@163.com
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20873107, 20373053).

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 Cs point groups while the [Ta2Rh4Cl4H8(CN)6]4- clusters are highly symmetric (C2h or C4v). The energy gaps (△EH-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