Department of Physical Chemistry, R. Bošković Institute, Bijenička 54, 10000 Zagreb, Croatia.
Phys Chem Chem Phys. 2019 Jan 23;21(4):1937-1951. doi: 10.1039/c8cp06103c.
This paper investigates the first sigma satellite band, which is by far the most prominent, in the valence photoelectron spectra for a set of isoelectronic diatomic molecules: carbon monoxide, carbon monosulfide, carbon monoselenide, silicon monoxide and boron monofluoride. In particular, we analyze the effect of the electronic structure, with the change of the atomic pair along the row and column of the periodic table on the position of the satellite peak as well as on the related dynamical observables profiles. For this investigation, highly correlated calculations have been performed on the primary ionic states and the satellite band for all the molecules considered. Cross sections for the primary ionic states, calculated using Dyson orbitals, have been compared with those obtained with Hartree-Fock and Density Functional Theory to probe the impact of the correlation in the bound states on the photoionization observables. Limitations of a simple intensity borrowing mechanism clearly result from the analysis of the satellite state, characterized by different features with respect to the relevant primary states.
本文研究了一系列等电子双原子分子的价光电离谱中迄今为止最显著的第一 sigma 卫星带：一氧化碳、碳单硫化物、碳单硒化物、一氧化硅和一氟化硼。特别地，我们分析了电子结构的影响，随着原子对沿着元素周期表的行和列的变化，对卫星峰的位置以及相关动力学观测值的分布的影响。对于这项研究，我们对所有考虑的分子的主要离子态和卫星带进行了高度相关的计算。使用 Dyson 轨道计算的初级离子态的截面已与使用 Hartree-Fock 和密度泛函理论获得的截面进行了比较，以探究束缚态中的相关性对光电离观测值的影响。从卫星态的分析中明显可以看出，简单的强度借用机制存在局限性，因为卫星态的特征与相关的主要态不同。
