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.

published proceedings

  • Inorg Chem

author list (cited authors)

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

citation count

  • 32

complete list of authors

  • Chen, Jie||Zhang, Hua||Tomov, Ivan V||Rentzepis, Peter M

publication date

  • March 2008