Acta Phys. -Chim. Sin. ›› 2014, Vol. 30 ›› Issue (12): 2233-2240.doi: 10.3866/PKU.WHXB201409301


A Comparative Ab initio Study of the Geometric and Electronic Structures of B2Au4, Al2Au4 and BAlAu4

YAO Wen-Zhi1, LU Zhang-Hui2, LI Si-Dian3   

  1. 1. School of Environmental and Municipal Engineering, North China University of Water Conservancy and Electric Power, Zhengzhou 450011, P. R. China;
    2. College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, P. R. China;
    3. Institute of Molecular Science, Shanxi University, Taiyuan 030001, P. R. China
  • Received:2014-06-23 Revised:2014-09-30 Published:2014-11-27
  • Contact: YAO Wen-Zhi, LU Zhang-Hui;
  • Supported by:

    The project was supported by the North China University ofWater Conservancy and Electric Power High-level Experts Scientific Research Foundation, China (201114), Henan Provincial Education Department, China (14A150024), Jiangxi Provincial Education Department, China (GJJ14230), Sponsored Program for Cultivating Youths of Outstanding Ability in Jiangxi Normal University, China, Young Scientist Foundation of Jiangxi Province, China (20133BCB23011),“Gan-Po Talent 555”Project of Jiangxi Province, China, and National Natural Science Foundation of China (21103074).


Au/H similarity is a hot topic in chemistry. Here, we report the theoretical prediction of new members of the Au/H analogy family: covalent B2Au4, ionic Al2Au4, and BAlAu4. A comparative study of the geometric and electronic structures of electron-deficient B2Au4, Al2Au4, and BAlAu4 was performed based on density and wave functional theories. Detailed orbital analyses, adaptive natural density partitioning (AdNDP), and electron localization function (ELF) analyses were performed. Ab initio theoretical evidence strongly suggests that the ground state of slightly distorted C2B2Au4 is a covalent complex containing two B―Au―B three centers-two electrons (3c-2e) bonds. Unexpectedly, C3vAl+(AlAu4)- and C3v Al+(BAu4)- are predicted to have a salt-like composition with three X―Au―Al 3c-2e bonds (X=Al in Al2Au4, X=B in BAlAu4). Al2Au4 and BAlAu4 represent the first examples of bridging gold bonds in ionic-deficient systems. The adiabatic and vertical detachment energies of the anions were calculated to facilitate their future experimental characterization. Bridging gold addressed in this work provides an interesting bonding mode for covalent and ionic-deficient systems, and may aid in designing new materials and catalysts with highly dispersed Au atoms.

Key words: Boron auride, Aluminum auride, Adaptive natural density partitioning, Electron localization function, Photoelectron spectroscopy


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