Pal R, Cui Li-Feng, Bulusu S, Zhai Hua-Jin, Wang Lai-Sheng, Zeng X C
Department of Chemistry, University of Nebraska-Lincoln, Lincoln, Nebraska 68588, USA.
J Chem Phys. 2008 Jan 14;128(2):024305. doi: 10.1063/1.2805386.
Photoelectron spectroscopy (PES) is combined with theoretical calculations to investigate the electronic and atomic structures of three doped aluminum clusters, MAl12- (M=Li, Cu, and Au). Well-resolved PES spectra have been obtained at two detachment photon energies, 266 nm (4.661 eV) and 193 nm (6.424 eV). Basin-hopping global optimization method in combination with density-functional theory calculations has been used for the structural searches. Good agreement between the measured PES spectra and theoretical simulations helps to identify the global minimum structures. It is found that LiAl12- (C(5nu)) can be viewed as replacing a surface Al atom by Li on an icosahedral Al13-, whereas Cu prefers the central site to form the encapsulated D3d-Cu@Al12-. For AuAl12- (C1), Au also prefers the central site, but severely distorts the Al12 cage due to its large size.
光电子能谱（PES）与理论计算相结合，用于研究三种掺杂铝簇MAl12-（M = Li、Cu和Au）的电子结构和原子结构。在两个分离光子能量，即266 nm（4.661 eV）和193 nm（6.424 eV）下，获得了分辨率良好的PES光谱。结合密度泛函理论计算的盆地跳跃全局优化方法已用于结构搜索。实测PES光谱与理论模拟之间的良好一致性有助于识别全局最小结构。研究发现，LiAl12-（C（5nu））可视为在二十面体Al13-上Li取代了一个表面Al原子，而Cu更倾向于占据中心位置形成包封的D3d-Cu@Al12-。对于AuAl12-（C1），Au也倾向于占据中心位置，但由于其尺寸较大，会严重扭曲Al12笼。
