Citation: YAO Wen-Zhi, LU Zhang-Hui, LI Si-Dian. A Comparative Ab initio Study of the Geometric and Electronic Structures of B₂Au₄, Al₂Au₄ and BAlAu₄[J]. Acta Physico-Chimica Sinica, ;2014, 30(12): 2233-2240. doi: 10.3866/PKU.WHXB201409301 shu

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

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 Date: 23 June 2014
Available Online: 30 September 2014
Fund Project: 华北水利水电学院高层次人才科学研究基金(201114) (201114) 河南省教育厅重点科技项目(14A150024) (14A150024) 江西省教育厅重点科技项目(GJJ14230) (GJJ14230) 江西师范大学青年英才培育计划资助项目, 江西省青年科学家培养对象(20133BCB23011) (20133BCB23011) 江西省赣鄱英才555 工程和国家自然科学基金(21103074)资助 (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, C_3vAl⁺(AlAu₄)^- and C_3v 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 ld bonds in ionic-deficient systems. The adiabatic and vertical detachment energies of the anions were calculated to facilitate their future experimental characterization. Bridging ld 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.
- Boron auride,
- Aluminum auride,
- Adaptive natural density partitioning,
- Electron localization function,
- Photoelectron spectroscopy
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A Comparative Ab initio Study of the Geometric and Electronic Structures of B2Au4, Al2Au4 and BAlAu4

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