Averkiev Boris B, Boldyrev Alexander I, Li Xi, Wang Lai-Sheng
Department of Chemistry and Biochemistry, Utah State University, 0300 Old Main Hill, Logan, UT 84322-0300, USA.
J Chem Phys. 2006 Sep 28;125(12):124305. doi: 10.1063/1.2335449.
The electronic and geometrical structures of three nitrogen-doped aluminum clusters, Al(x)N(-) (x=3-5), are investigated using photoelectron spectroscopy and ab initio calculations. Well-resolved photoelectron spectra have been obtained for the nitrogen-doped aluminum clusters at four photon energies (532, 355, 266, and 193 nm). Global minimum structure searches for Al(x)N(-) (x=3-5) and their corresponding neutrals are performed using several theoretical methods. Vertical electron detachment energies are calculated using three different methods for the lowest energy structures and low-lying isomers are compared with the experimental observations. Planar structures have been established for all the three Al(x)N(-) (x=3-5) anions from the joint experimental and theoretical studies. For Al(5)N(-), a low-lying nonplanar isomer is also found to contribute to the experimental spectra, signifying the onset of two-dimensional to three-dimensional transition in nitrogen-doped aluminum clusters. The chemical bonding in all the planar clusters has been elucidated on the basis of molecular orbital and natural bond analyses.
利用光电子能谱和从头算方法研究了三种氮掺杂铝簇Al(x)N(-)（x = 3 - 5）的电子结构和几何结构。在四个光子能量（532、355、266和193 nm）下获得了氮掺杂铝簇的分辨良好的光电子能谱。使用几种理论方法对Al(x)N(-)（x = 3 - 5）及其相应的中性体进行了全局最小结构搜索。对最低能量结构使用三种不同方法计算垂直电子脱离能，并将低位异构体与实验观测结果进行比较。通过联合实验和理论研究确定了所有三种Al(x)N(-)（x = 3 - 5）阴离子的平面结构。对于Al(5)N(-)，还发现一个低位非平面异构体对实验光谱有贡献，这表明在氮掺杂铝簇中二维到三维的转变开始。基于分子轨道和自然键分析阐明了所有平面簇中的化学键。
