Transient structures and kinetics of the ferrioxalate redox reaction studied by time-resolved EXAFS, optical spectroscopy, and DFT

作者：Chen Jie; Zhang Hua; Tomov Ivan V; Wolfsherg Max; Ding Xunliang; Rentzepis Peter M^*

来源：Journal of Physical Chemistry A, 2007, 111(38): 9326-9335.

DOI：10.1021/jp0733466

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

• 出版日期2007-9-27
• 单位北京师范大学