Hua Weijie, Tian Guangjun, Luo Yi
Department of Applied Physics, School of Science, Nanjing University of Science and Technology, 210094 Nanjing, China.
Key Laboratory for Microstructural Material Physics of Hebei Province, School of Science, Yanshan University, Qinhuangdao 066004, China.
Phys Chem Chem Phys. 2020 Sep 16;22(35):20014-20026. doi: 10.1039/d0cp02970j.
An interface between our in-house DynaVib package and quantum chemistry software Gamess-US is implemented for computing vibrationally-resolved K-edge X-ray photoelectron spectra (XPS) of molecules at the density functional theory level with both the full (FCH) and equivalent (ECH, or Z+1) core-hole approximations. To assess the influence of theoretical parameters (core-hole methods, vibronic coupling models, and basis sets), vibrationally-resolved C1s XPS of six simple cyclic molecules [furan, pyrrole, thiophene; benzene (C6H6 and C6D6); pyridine] were evaluated in the gas phase by both core-hole methods in combination with two time-independent vibronic coupling models, the Duschinsky rotation (DR) method and the linear coupling model (LCM). We achieved excellent/acceptable performance for FCH/Z+1 simulations in comparison with experiments. The most accurate method FCH-DR correctly reproduced all experimental features and gave an accuracy of ca. 0.2 eV in absolute binding energies (BEs). The choice of the vibronic model is less sensitive to that of electronic structure method. Results indicate that Z+1 overestimates the core-hole effect on the geometry of the ionization state.
我们在内部的DynaVib软件包和量子化学软件Gamess-US之间实现了一个接口，用于在密度泛函理论水平上，使用全芯孔（FCH）近似和等效芯孔（ECH，或Z + 1）近似来计算分子的振动分辨K边X射线光电子能谱（XPS）。为了评估理论参数（芯孔方法、振动电子耦合模型和基组）的影响，通过两种芯孔方法结合两种与时间无关的振动电子耦合模型——杜申斯基旋转（DR）方法和线性耦合模型（LCM），在气相中对六种简单环状分子[呋喃、吡咯、噻吩；苯（C6H6和C6D6）；吡啶]的振动分辨C1s XPS进行了评估。与实验相比，我们在FCH/Z + 1模拟中获得了优异/可接受的性能。最精确的方法FCH-DR正确地再现了所有实验特征，并且在绝对结合能（BE）方面给出了约0.2 eV的精度。振动电子模型的选择对电子结构方法的选择不太敏感。结果表明，Z + 1高估了芯孔对电离态几何结构的影响。
