title: Bridging gold in electron-deficient Al2Au(n)(0/-) and BAlAu(n)(0/-) (n = 1-3) clusters.
abstract: The geometrical and electronic structures of the electron-deficient dialuminum aurides Al2Aun(0/-) and hybrid boron-aluminum aurides BAlAun(0/-) (n = 1-3) are systematically investigated based on the density and wave function theories. Ab initio theoretical evidence strongly suggests that bridging gold atoms exist in the ground states of C2v Al2Au(-) ((3)B1), C2v Al2Au ((2)B1), C2v Al2Au2(-) ((2)A1), C2v Al2Au2 ((1)A1), Cs Al2Au3(-) ((1)A'), and D3h Al2Au3 ((2)A1), which prove to possess an Al-Au-Al τ bond. For BAlAun(0/-) (n = 1-3) mixed clusters, bridging B-Au-Al units only exist in Cs BAlAu3(-) ((1)A') and Cs BAlAu3 ((2)A'), whereas Cs BAlAu(-) ((3)A''), Cs BAlAu ((2)A''), Cs BAlAu2(-) ((2)A'), and Cs BAlAu2 ((1)A') do not possess a bridging gold, as demonstrated by the fact that B-Al and B-Au exhibit significantly stronger electronic interaction than Al-Au in the same clusters. Orbital analyses indicate that Au 6s contributes approximately 98%-99% to the Au-based orbital in these Al-Au-Al/B-Au-Al interactions, whereas Au 5d contributes 1%-2%. The adiabatic and vertical detachment energies of Al2Aun(-) (n = 1-3) are calculated to facilitate future experimental characterizations. The results obtained in this work establish an interesting τ bonding model (Al-Au-Al/B-Au-Al) for electron-deficient systems in which Au 6s plays a major factor.
authors.affiliation: Department of Environmental and Municipal Engineering, North China University of Water Conservancy and Electric Power , Zhengzhou, 450011, China.
authors.forename: Wen-Zhi
authors.initials: WZ
authors.lastname: Yao
authors.forename: Bing-Tao
authors.initials: BT
authors.lastname: Liu
authors.forename: Zhang-Hui
authors.initials: ZH
authors.lastname: Lu
authors.forename: Si-Dian
authors.initials: SD
authors.lastname: Li