科研之友
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摘要
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 ELF) analyses were performed. Ab initio theoretical evidence strongly suggests that the ground state of slightly distorted C-2 B2Au4 is a covalent complex containing two B-Au-B three centers-two electrons (3c-2e) bonds. Unexpectedly, C-3v Al+(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 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.
