title: Transition from exohedral to endohedral structures of AuGen(-) (n = 2-12) clusters: photoelectron spectroscopy and ab initio calculations.
abstract: Gold-doped germanium clusters, AuGen(-) (n = 2-12), were investigated by using anion photoelectron spectroscopy in combination with ab initio calculations. Their geometric structures were determined by comparison of the theoretical calculations with the experimental results. The results show that the most stable isomers of AuGen(-) with n = 2-10 are all exohedral structures with the Au atom capping the vertex, edge or face of Gen clusters, while AuGe11(-) is found to be the critical size of the endohedral structure. Interestingly, AuGe12(-) has an Ih symmetric icosahedral structure with the Au atom located at the center. The molecular orbital analysis of the AuGe12(-) cluster suggests that the interactions between the 5d orbitals of the Au atom and the 4s4p hybridized orbitals of the Ge atoms may stabilize the Ih symmetric icosahedral cage and promote the Au atom to be encapsulated in the cage of Ge12. The NICS(0) and NICS(1) values are calculated to be -143.7 ppm and -36.3 ppm, respectively, indicating that the icosahedral AuGe12(-) cluster is significantly aromatic.
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. xlxu@iccas.ac.cn zhengwj@iccas.ac.cn.
authors.forename: Sheng-Jie
authors.initials: SJ
authors.lastname: Lu
authors.affiliation: Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
authors.forename: Lian-Rui
authors.initials: LR
authors.lastname: Hu
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. xlxu@iccas.ac.cn zhengwj@iccas.ac.cn.
authors.forename: Xi-Ling
authors.initials: XL
authors.lastname: Xu
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. xlxu@iccas.ac.cn zhengwj@iccas.ac.cn.
authors.forename: Hong-Guang
authors.initials: HG
authors.lastname: Xu
authors.affiliation: Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
authors.forename: Hui
authors.initials: H
authors.lastname: Chen
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. xlxu@iccas.ac.cn zhengwj@iccas.ac.cn.
authors.forename: Wei-Jun
authors.initials: WJ
authors.lastname: Zheng