Research Group of Theoretical Chemistry and Molecular Modelling, Hasselt University, Agoralaan Gebouw D, B-3590 Diepenbeek, Belgium.
J Phys Chem A. 2010 Sep 2;114(34):9374-87. doi: 10.1021/jp105551j.
An extensive study, throughout the valence region, of the electronic structure, ionization spectrum, and electron momentum distributions of norbornadiene is presented, on the ground of accurate calculations of valence one-electron and shake-up ionization energies and of the related Dyson orbitals, using one-particle Green's function (1p-GF) theory in conjunction with the so-called third-order algebraic diagrammatic construction scheme [ADC(3)]. Comparison is made with results obtained from standard (B3LYP) Kohn-Sham orbitals and measurements employing electron momentum spectroscopy, taking into account the contamination of inner- and outer-valence spectral bands by numerous shake-up states. Four relatively intense shake-up lines at 12.1, 16.4, 17.6, and 17.8 eV are found to yield recognizable spectral fingerprints in the EMS experiments. Valence bands at electron binding energies larger than 20 eV are subject to a complete breakdown of the orbital picture of ionization.
本文基于对价层单电子电离能和振激电离能以及相关狄森轨道的精确计算，采用单粒子格林函数（1p-GF）理论结合所谓的三阶代数图式构造方案（ADC(3)），对降蒈二烯的电子结构、电离光谱和电子动量分布进行了广泛的研究。将其与使用电子动量谱进行测量的标准（B3LYP）Kohn-Sham 轨道结果进行了比较，并考虑了内价和外价谱带中大量振激态的污染。在 EMS 实验中发现，在 12.1、16.4、17.6 和 17.8 eV 处有四条相对较强的振激线，它们产生可识别的光谱指纹。电子结合能大于 20 eV 的价带的电离轨道图像完全失效。
