Abstract Like other spectroscopic methods XPS and AES show characteristic chemical shifts depending on the elemental matrix of a compound, however, a satisfactory rationalization of the variance of such values is often difficult. By an extension of a previous approach we present a theory in a unifying equation which combines several parameters - some of them resulting from DFT calculations - which influence the energy of the outgoing electrons and thereby seemingly the binding energy. By calculating Bader charges, atomic volumes and site potentials we have produced a data basis for a set of chalcogenides and halides of Ba, Zn, Pb and Cu to rationalize the spread of measured binding energies and Auger energies. It has thereby become possible to quantify different factors separately which bias the measurement of the kinetic energies of the outgoing core electrons, both the photo-emitted and the Auger electrons. Such an analysis can also trace special features of an open-shell configuration and even show up effects of a semiconductor-type.

中文翻译：

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物理遗传学：杂交密度泛函理论和 X 射线光电子能谱使固体化合物中结合能的化学位移合理化

摘要 与其他光谱方法一样，XPS 和 AES 显示出取决于化合物元素矩阵的特征化学位移，但是，这些值的方差的合理化通常很困难。通过对先前方法的扩展，我们在一个统一方程中提出了一个理论，该方程结合了几个参数——其中一些是由 DFT 计算得出的——这些参数影响出射电子的能量，从而影响结合能。通过计算贝德电荷、原子体积和位点电位，我们为一组 Ba、Zn、Pb 和 Cu 的硫属化物和卤化物生成了数据基础，以合理化测量结合能和俄歇能的传播。从而有可能分别量化不同的因素，这些因素会偏置出射核心电子的动能测量，包括光发射电子和俄歇电子。这种分析还可以追踪开壳配置的特殊特征，甚至可以显示半导体类型的影响。