Transient Structures and Kinetics of the Ferrioxalate Redox Reaction Studied by Time-Resolved EXAFS, Optical Spectroscopy, and DFT

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• 作者：Jie Chen ; Hua Zhang ; Ivan V. Tomov ; Max Wolfsberg ; Xunliang Ding ; Peter M. Rentzepis
• 刊名：Journal of Physical Chemistry A
• 出版年：2007
• 出版时间：September 27, 2007
• 年：2007
• 卷：111
• 期：38
• 页码：9326 - 9335
• 全文大小：237K
• 年卷期：v.111,no.38(September 27, 2007)
• ISSN：1520-5215

文摘

The photoredox reaction transients of ferrioxalate in water have been studied by means of time-resolvedEXAFS and ultrafast optical transient spectroscopy. The transient spectra and kinetics have been measuredfrom the femtosecond to millisecond range, and the Fe-O bond lengths of the ferrioxalate redox reactiontransients have been determined with 2 ps time resolution and 0.04 Å accuracy. These data in conjunctionwith quantum-chemistry DFT and UHF calculations were used to formulate a mechanism for the Fe(III) toFe(II) redox reaction where dissociation precedes electron transfer. In addition, radical scavenging experimentssupport the mechanism proposed.