Electron momentum spectroscopy study on valence electronic structures of ethylamine.
Electron momentum spectroscopy study on valence electronic structures of ethylamine.
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DOI：
10.1021/jp808281w
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发表时间：
2009-01
期刊：
影响因子：
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通讯作者：
M. Yan;X. Shan;Fang Wu;X. Xia;Kedong Wang;K. Xu;Xiangjun Chen
中科院分区：
文献类型：
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作者：
M. Yan;X. Shan;Fang Wu;X. Xia;Kedong Wang;K. Xu;Xiangjun Chen
用（e，2 e）电子动量谱测量了气态乙胺的价壳层结合能谱和电子动量分布。当考虑到反式构象的Boltzmann加权丰度为39%和两种等价的gauche构象的Boltzmann加权丰度为61%时，采用B3 LYP方法在6-311++G** 和aug-cc-pVTZ基组下计算得到的所有价轨道的热平均电子动量分布与实验结果吻合较好，支持反式构象更稳定的观点.此外，对反式构象分子的2a“和7a”轨道进行了重新排序，并通过比较相应分子轨道的实验动量分布和理论动量分布，确认了在13.7 eV附近的电离带，这在以前的文献中是不确定的.此外，首次报道了内价轨道的电离势和极强度。
The valence-shell binding energy spectra and electron momentum profiles of gaseous ethylamine are measured by (e, 2e) electron momentum spectroscopy. When taking into account the Boltzmann-weighted abundance of 39% for trans and 61% for two equivalent gauche conformers coexisted in ethylamine, the thermally averaged electron momentum profiles for all valence orbitals calculated using B3LYP method with 6-311++G** and aug-cc-pVTZ basis sets reproduce the experimental ones well, which supports that the trans conformer is more stable. In addition, the controversial ordering of 2a'' and 7a' orbitals for the trans conformer is reassigned and an ionization band at about 13.7 eV, which was uncertain in previous literatures, is confirmed by comparing the experimental momentum profiles with the theoretical ones for the respective molecular orbitals. Furthermore, the ionization potentials and pole strengths for the inner valence orbitals are reported for the first time.