Electronic Structure of Third-Row Elements in Different Local Symmetries Studied by Valence-to-Core X-ray Emission Spectroscopy

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• 作者：Marko Petric ; Rok Bohinc ; Klemen Bučar ; Stanisław H. Nowak ; Matjaž Žitnik ; Matjaž Kavčič
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：June 6, 2016
• 年：2016
• 卷：55
• 期：11
• 页码：5328-5336
• 全文大小：448K
• 年卷期：0
• ISSN：1520-510X

文摘

The electronic structure of phosphorus, sulfur, and chlorine in compounds with T_d and C_3v local symmetries was studied with high-resolution Kβ X-ray emission spectroscopy (XES) in the tender X-ray range. Measured spectra are compared to the results of ab initio quantum chemical calculations based on density functional theory (DFT). The spectral structure is reproduced by the model spectra of isolated XO₄^n– and XO₃^n– (X = P, S, or Cl) anions incorporating only the first coordination sphere around the central atom. The main spectral components can be explained by the molecular orbital theory. Finally, the potential of XES spectroscopy combined with DFT calculations to study the electronic structure of third-row elements in a slightly larger molecule is investigated.