title: Electron transfer mechanism and photochemistry of ferrioxalate induced by excitation in the charge transfer band.
abstract: The photoredox reaction of ferrioxalate after 266/267 nm excitation in the charge transfer band has been studied by means of ultrafast extended X-ray absorption fine structure (EXAFS) analysis, optical transient spectroscopy, and quantum chemistry calculations. The Fe-O bond length changes combined with the transient spectra and kinetics have been measured and in combination with ultrahigh frequency density functional theory (UHF/DFT) calculations are used to determine the photochemical mechanism for the Fe(III) to Fe(II) redox reaction. The present data and the results obtained with 266/267 nm excitations strongly suggest that the primary reaction is the dissociation of the Fe-O bond before intramolecular electron transfer occurs. Low quantum yield electron photodetachment from ferrioxalate has also been observed.
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: Peter M
authors.initials: PM
authors.lastname: Rentzepis
mesh_terms: D004583:Electrons; D007700:Kinetics; D010070:Oxalates / Q000737:chemistry*; D010777:Photochemistry / Q000379:methods; D012997:Solvents; D013053:Spectrophotometry
chemical_list: D010070:Oxalates; D012997:Solvents