Transient structures and kinetics of the ferrioxalate redox reaction studied by time-resolved EXAFS, optical spectroscopy, and DFT.
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 A 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.
Chen
Jie
J
Department of Chemistry, University of California, Irvine, California 92697, USA.
Zhang
Hua
H
Tomov
Ivan V
IV
Wolfsberg
Max
M
Ding
Xunliang
X
Rentzepis
Peter M
PM