Dolgounitcheva O, Zakrzewski V G, Ortiz J V
Department of Chemistry, Kansas State University, Manhattan, Kansas 66506-3701, USA.
J Phys Chem A. 2005 Dec 22;109(50):11596-601. doi: 10.1021/jp0538060.
Ab initio electron propagator methods are applied to the prediction, assignment, and interpretation of the valence photoelectron spectra of free base porphine and of magnesium and zinc porphyrins. Tests of various approximate self-energies, including the partial third (P3), the outer valence Green's function, and the nondiagonal, renormalized second-order (NR2) methods are performed. Basis set effects and reduced active orbital spaces are examined as well. The P3 method and the one-electron picture of ionization that accompanies it are validated for the first two cationic states and for states with sigma holes that are localized in nitrogen, lone pair regions. In the remaining pi-hole states, there is significant shake-up character and NR2 results provide useful diagnostics of correlation effects.
从头算电子传播子方法被应用于对游离碱卟吩以及镁卟啉和锌卟啉的价光电子能谱进行预测、归属和解释。对各种近似自能进行了测试，包括部分三阶（P3）、外层价格林函数以及非对角、重整化二阶（NR2）方法。还研究了基组效应和缩减的活性轨道空间。P3方法及其伴随的单电子电离图像在前两个阳离子态以及氮孤对区域存在σ空穴的态中得到了验证。在其余的π空穴态中，存在显著的振激特征，NR2结果为相关效应提供了有用的诊断。
