Atkins Andrew J, Bauer Matthias, Jacob Christoph R
Karlsruhe Institute of Technology (KIT), Center for Functional Nanostructures and Institute of Physical Chemistry, Wolfgang-Gaede-Str. 1a, 76131 Karlsruhe, Germany.
Phys Chem Chem Phys. 2015 Jun 7;17(21):13937-48. doi: 10.1039/c5cp01045d. Epub 2015 May 7.
We apply high-energy-resolution fluorescence-detected (HERFD) X-ray absorption near-edge spectroscopy (XANES) to study iron carbonyl complexes. Mono-, bi-, and tri-nuclear carbonyl complexes and pure carbonyl complexes as well as carbonyl complexes containing hydrocarbon ligands are considered. The HERFD-XANES spectra reveal multiple pre-edge peaks with individual signatures for each complex, which could not be detected previously with conventional XANES spectroscopy. These peaks are assigned and analysed with the help of TD-DFT calculations. We demonstrate that the pre-edge peaks can be used to distinguish the different types of iron-iron interactions in carbonyl complexes. This opens up new possibilities for applying HERFD-XANES spectroscopy to probe the electronic structure of iron catalysts.
我们应用高能量分辨率荧光探测（HERFD）X射线吸收近边光谱（XANES）来研究羰基铁配合物。研究对象包括单核、双核和三核羰基配合物、纯羰基配合物以及含有烃类配体的羰基配合物。HERFD-XANES光谱揭示了每个配合物具有独特特征的多个预边峰，而这些峰在以前的传统XANES光谱中无法检测到。借助TD-DFT计算对这些峰进行了归属和分析。我们证明，预边峰可用于区分羰基配合物中不同类型的铁-铁相互作用。这为应用HERFD-XANES光谱探测铁催化剂的电子结构开辟了新的可能性。
