Nature of the Chemical Bond of Aqueous Fe2+ Probed by Soft X-ray Spectroscopies and ab Initio Calculations

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• 作者：Kaan Atak ; Sergey I. Bokarev ; Malte Gotz ; Ronny Golnak ; Kathrin M. Lange ; Nicholas Engel ; Marcus Dantz ; Edlira Suljoti ; Oliver K眉hn ; Emad F. Aziz
• 刊名：Journal of Physical Chemistry B
• 出版年：2013
• 出版时间：October 17, 2013
• 年：2013
• 卷：117
• 期：41
• 页码：12613-12618
• 全文大小：307K
• 年卷期：v.117,no.41(October 17, 2013)
• ISSN：1520-5207

文摘

Aqueous iron(II) chloride is studied by soft X-ray absorption, emission, and resonant inelastic Raman scattering techniques on the Fe L-edge and O K-edge using the liquid-jet technique. Soft X-ray spectroscopies allow in situ and atom-specific probing of the electronic structure of the aqueous complex and thus open the door for the investigation of chemical bonding and molecular orbital mixing. In this work, we combine theoretical ab initio restricted active space self-consistent field and local atomic multiplet calculations with experimental soft X-ray spectroscopic methods for a description of the local electronic structure of the aqueous ferrous ion complex. We demonstrate that the atomic iron valence final states dominate the resonant inelastic X-ray scattering spectra of the complex over the ligand-to-metal charge transfer transitions, which indicates a weak interaction of Fe²⁺ ion with surrounding water molecules. Moreover, the oxygen K-edge also shows only minor changes due to the presence of Fe²⁺ implying a small influence on the hydrogen-bond network of water.