Valence-to-Core X-ray Emission Spectroscopy: A Sensitive Probe of the Nature of a Bound Ligand
Valence-to-Core X-ray Emission Spectroscopy: A Sensitive Probe of the Nature of a Bound Ligand
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DOI：
10.1021/ja200560z
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发表时间：
2011-04-13
影响因子：
15
通讯作者：
DeBeer, Serena
中科院分区：
文献类型：
--
作者：
Pollock, Christopher J.;DeBeer, Serena
探讨了铁的K-βX射线发射光谱(XES)对结合配体性质(Sigma供体、pi供体和pi接受体)的敏感性。采用实验和理论相结合的方法，用密度泛函方法阐明了配体对光谱的影响，并指定了光谱强度机制。了解对光谱的各种贡献可以更深入地了解光谱特征，并表明该方法对相互作用配体的身份的敏感性。XES在鉴定非血红素铁酶中间物种方面的潜力被强调。
The sensitivity of iron K beta X-ray emission spectroscopy (XES) to the nature of the bound ligands (sigma-donating, pi-donating, and pi-accepting) has been explored. A combination of experiment and theory has been employed, with a DFT approach being utilized to elucidate ligand effects on the spectra and to assign the spectral intensity mechanisms. Knowledge of the various contributions to the spectra allows for a deeper understanding of spectral features and demonstrates the sensitivity of this method to the identity of the interacting ligands. The potential of XES for identifying intermediate species in nonheme iron enzymes is highlighted.