Electron transfer mechanism and photochemistry of ferrioxalate induced by excitation in the charge transfer band.
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.
Chen
Jie
J
Department of Chemistry, University of California, Irvine, California 92697, USA.
Zhang
Hua
H
Tomov
Ivan V
IV
Rentzepis
Peter M
PM
D004583:Electrons; D007700:Kinetics; D010070:Oxalates / Q000737:chemistry*; D010777:Photochemistry / Q000379:methods; D012997:Solvents; D013053:Spectrophotometry
D010070:Oxalates; D012997:Solvents