On the electronic structure and chemical bonding in the tantalum trimer cluster.
On the electronic structure and chemical bonding in the tantalum trimer cluster.
复制标题
DOI：
10.1021/jp806166h
复制
发表时间：
2008-10
期刊：
影响因子：
--
通讯作者：
Bin Wang;Hua‐Jin Zhai;Xin Huang;Lai‐Sheng Wang
中科院分区：
文献类型：
--
作者：
Bin Wang;Hua‐Jin Zhai;Xin Huang;Lai‐Sheng Wang
利用光电子能谱和密度泛函理论计算研究了Ta 3（-）团簇的电子结构和化学键。在四个光子能量：532，355，266和193 nm处获得Ta 3（-）的光电子能谱。虽然拥挤的光谱观察到在高的电子结合能，几个低洼的电子跃迁很好地解决，并与理论计算相比。Ta 3的电子亲和势为1.35 +/-0.03eV。在B3 LYP/Stuttgart +2f 1g水平上对Ta 3和Ta 3（-）的基态和低位异构体进行了密度泛函计算. Ta 3（-）阴离子的基态是一个具有D3 h对称性的五重态（（5）A1 '），而中性Ta 3的基态则有两个近似等能态C2 v（（4）A1）和D3 h（（6）A1'）竞争.通过详细的分子轨道分析，阐明了Ta 3（-）的化学键合，发现Ta 3（-）具有多个d轨道芳香性，这与其高度对称的D3 h结构相当.
The electronic structure and chemical bonding in the Ta 3 (-) cluster are investigated using photoelectron spectroscopy and density functional theory calculations. Photoelectron spectra are obtained for Ta 3 (-) at four photon energies: 532, 355, 266, and 193 nm. While congested spectra are observed at high electron binding energies, several low-lying electronic transitions are well resolved and compared with the theoretical calculations. The electron affinity of Ta 3 is determined to be 1.35 +/- 0.03 eV. Extensive density functional calculations are performed at the B3LYP/Stuttgart +2f1g level to locate the ground-state and low-lying isomers for Ta 3 and Ta 3 (-). The ground-state for the Ta 3 (-) anion is shown to be a quintet ( (5)A 1') with D 3 h symmetry, whereas two nearly isoenergetic states, C 2 v ( (4)A 1) and D 3 h ( (6)A 1'), are found to compete for the ground-state for neutral Ta 3. A detailed molecular orbital analysis is performed to elucidate the chemical boding in Ta 3 (-), which is found to possess multiple d-orbital aromaticity, commensurate with its highly symmetric D 3 h structure.