Accurate treatment of electron correlation and spin-orbit coupling is essential for understanding the electronic structure and spectroscopy of high-spin, open-shell transition metal dihalides. The experimental photoelectron spectra of MnX₂, X= Cl, Br, I, have been interpreted on the basis of multi-configurational ab initio electronic structure calculations. The intensity of the photoelectron bands have been calculated from the norms of the Dyson orbitals, which represent the transition probability to a particular ionic state from a given starting state. The present study provides a detailed account of the contribution of the one- and two-electron transitions in the experimental photoelectron spectra of the title molecules and outlines the nature of the photoelectron bands in terms of the closely spaced quintet and septet states of the cationic species.

正确处理电子相关性和自旋轨道耦合对于理解高自旋，开壳过渡金属二卤化物的电子结构和光谱学至关重要。MnX ₂的实验光电子能谱在多构型从头算电子结构计算的基础上解释了X，Cl，Br，I。根据戴森轨道的范数计算了光电子能带的强度，戴森轨道的范数表示从给定的起始状态到特定离子态的跃迁几率。本研究详细说明了标题分子的实验光电子能谱中一电子和二电子跃迁的贡献，并根据阳离子物种的紧密间隔的五重态和七态确定了光电子能带的性质。 。