Electron Transfer Mechanism and Photochemistry of Ferrioxalate Induced by Excitation in the Charge Transfer Band Academic Article uri icon

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.

author list (cited authors)

  • Chen, J., Zhang, H., Tomov, I. V., & Rentzepis, P. M.

publication date

  • January 1, 2008 11:11 AM