Two-Dimensional Penning Ionization Electron Spectroscopy of Open-Shell Metallocenes: Outer Valence Ionic States of Vanadocene and Nickelocene
Two-Dimensional Penning Ionization Electron Spectroscopy of Open-Shell Metallocenes: Outer Valence Ionic States of Vanadocene and Nickelocene
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开壳茂金属的二维潘宁电离电子能谱：钒二茂和镍茂的外价离子态
DOI：
10.1021/jp310308k
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发表时间：
2013
期刊：
影响因子：
--
通讯作者：
and Koichi Ohno
中科院分区：
文献类型：
--
作者：
Naoki Kishimoto;Miku Kimura;and Koichi Ohno
为了研究开壳层双烯的外层价离子态，我们应用二维碰撞能/电子能分辨的Penning电离电子能谱（2D-PIES）和高水平的从头算分子轨道计算方法研究了亚稳态He ~*（23 S）激发态原子碰撞过程（电子传播子的部分三阶准粒子理论（P3））到二茂钒（4A 2g）和二茂镍（3A 2g）的中性基态电离。Penning电离电子/He I紫外光电子能谱的计算结果与P3计算结果一致，但PIES观测到的电子相关带除外。部分潘宁电离截面（CEDPICS）的负碰撞能量依赖性表明分子周围与He*（23 S）的吸引相互作用。用Li（22 S）代替He*（23 S）计算He*（23 S）与开壳层双烯相互作用的模型势的结果不能解释在PIES中观察到的强负CEDPICS带。
In order to investigate outer valence ionic states of open-shell metallocenes, we have applied two-dimensional collision-energy/electron-energy-resolved Penning ionization electron spectroscopy (2D-PIES) upon collision with metastable He*(23S) excited atoms as well as a high level ab initio molecular orbital calculation (the partial third-order quasiparticle theory of the electron propagator (P3)) to ionization from neutral ground states of vanadocene (4A2g) and nickelocene (3A2g). Assignments of observed Penning ionization electron/He I ultraviolet photoelectron spectra were consistent with the P3 calculation results for ionization of α and β spin electrons except for electron correlation bands observed by PIES. Negative collision energy dependence of partial Penning ionization cross-sections (CEDPICS) indicate attractive interaction with He*(23S) around the molecule. Results by model potential calculation utilizing Li(22S) instead of He*(23S) for interaction between He*(23S) and open-shell metallocenes do not explain the strong negative CEDPICS of the bands observed in PIES.