从头计算方法比较研究B2Au4, Al2Au4和BAlAu4的几何和电子结构

引用本文: 姚文志, 卢章辉, 李思殿. 从头计算方法比较研究B₂Au₄, Al₂Au₄和BAlAu₄的几何和电子结构[J]. 物理化学学报, 2014, 30(12): 2233-2240. doi: 10.3866/PKU.WHXB201409301 shu

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

从头计算方法比较研究B₂Au₄, Al₂Au₄和BAlAu₄的几何和电子结构

基金项目:
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)

摘要:

Au/H 相似性的研究是现代化学中的一个热门话题. 我们从理论上报道Au/H 相似的新成员: 共价化合物B₂Au₄, 离子化合物Al₂Au₄和BAlAu₄. 采用密度泛函和波函数理论方法对比研究了缺电子体系B₂Au₄、Al₂Au₄和BAlAu₄的几何和电子结构. 详细讨论了它们基态结构的轨道、适应性自然密度划分(AdNDP)和电子局域函数(ELF)分析. 计算结果表明稍微扭曲变形的C₂B₂Au₄是基态结构, 在这个共价化合物中含有两个B―Au―B三中心二电子(3c-2e)键. 然而C_3v Al⁺(AlAu₄)^-和C_3v Al⁺(BAu₄)^-被研究证明是含有三个X―Au―Al 三中心二电子键的类盐化合物(在Al₂Au₄中X=Al, BAlAu₄中X=B). Al₂Au₄和BAlAu₄是至今为止首例报道的在离子缺电子体系中含有金桥键的化合物. 同时计算了B₂Au₄^-、Al₂Au₄^- 和BAlAu₄^- 阴离子基态结构的绝热剥离能和垂直剥离能, 为实验表征提供依据. 文中报道的金桥键为共价键和离子键相结合的缺电子体系提供了一个有趣的键合模式, 有助于设计含有高度分散金原子的新材料和催化剂.

关键词:

English

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: 27 November 2014
Fund Project:
华北水利水电学院高层次人才科学研究基金(201114)

河南省教育厅重点科技项目(14A150024)

江西省教育厅重点科技项目(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)

江西省赣鄱英才555 工程和国家自然科学基金(21103074)资助

Abstract:

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.

Key words:

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从头计算方法比较研究B₂Au₄, Al₂Au₄和BAlAu₄的几何和电子结构

English

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

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