Electronic Structure of Hemin in Solution Studied by Resonant X-ray Emission Spectroscopy and Electronic Structure Calculations

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• 作者：Kaan Atak ; Ronny Golnak ; Jie Xiao ; Edlira Suljoti ; Mika Pfl眉ger ; Tim Brandenburg ; Bernd Winter ; Emad F. Aziz
• 刊名：Journal of Physical Chemistry B
• 出版年：2014
• 出版时间：August 21, 2014
• 年：2014
• 卷：118
• 期：33
• 页码：9938-9943
• 全文大小：324K
• ISSN：1520-5207

文摘

Resonant inelastic X-ray scattering spectra at the iron L-edge from hemin in dimethyl sulfoxide liquid solution are reported. Our experiments, which are interpreted with the help of electronic structure calculations, support earlier assignments of hemin鈥搒olvent interactions, including the iron spin state and the role of the chloride ligand obtained from a total fluorescence yield study. The analysis of the explicit radiative relaxation channels of 2p core-level excited iron, explored in the present work, allows for a rather quantitative assignment of the orbitals involved in the excitation鈥揹eexcitation process of the core-excited hemin in solution. We specifically distinguish between contributions of partially and fully occupied valence orbitals to the broad X-ray emission band. In addition, our calculations reveal a detailed picture of the character of these orbitals.