Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 111, Issue 38, Pages 9326-9335Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp0733466
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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.
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