物理化学学报 >> 2014, Vol. 30 >> Issue (12): 2233-2240.doi: 10.3866/PKU.WHXB201409301

理论与计算化学 上一篇    下一篇

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

姚文志1, 卢章辉2, 李思殿3   

  1. 1. 华北水利水电大学环境与市政工程学院, 郑州 450011;
    2. 江西师范大学化学与化学工程学院, 南昌 330022;
    3. 山西大学分子科学研究所, 太原 030001
  • 收稿日期:2014-06-23 修回日期:2014-09-30 发布日期:2014-11-27
  • 通讯作者: 姚文志, 卢章辉 E-mail:yaowenzhi-1982@163.com;luzh@jxnu.edu.cn
  • 基金资助:

    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

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 E-mail:yaowenzhi-1982@163.com;luzh@jxnu.edu.cn
  • 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).

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C3v Al+(AlAu4)-C3v 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: 硼金团簇, 铝金团簇, 适应性自然密度划分, 电子局域函数, 光电子能谱

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, 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

MSC2000: 

  • O641