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