Time-Resolved X-ray Spectroscopy in the Water Window: Elucidating Transient Valence Charge Distributions in an Aqueous Fe(II) Complex

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• 作者：Benjamin E. Van Kuiken ; Hana Cho ; Kiryong Hong ; Munira Khalil ; Robert W. Schoenlein ; Tae Kyu Kim ; Nils Huse
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2016
• 出版时间：February 4, 2016
• 年：2016
• 卷：7
• 期：3
• 页码：465-470
• 全文大小：327K
• ISSN：1948-7185

文摘

Time-resolved nitrogen-1s spectroscopy in the X-ray water window is presented as a novel probe of metal–ligand interactions and transient states in nitrogen-containing organic compounds. New information on iron(II) polypyridyl complexes via nitrogen core-level transitions yields insight into the charge density of the photoinduced high-spin state by comparing experimental results with time-dependent density functional theory. In the transient high-spin state, the 3d electrons of the metal center are more delocalized over the nearest-neighbor nitrogen atoms despite increased bond lengths. Our findings point to a strong coupling of electronic states with charge-transfer character, facilitating the ultrafast intersystem crossing cascade in these systems. The study also highlights the importance of local charge density measures to complement chemical interaction concepts of charge donation and back-bonding with molecular orbital descriptions of states.