Transient Structures and Kinetics of the Ferrioxalate Redox Reaction Studied by Time-Resolved EXAFS, Optical Spectroscopy, and DFT
- 29 August 2007
- journal article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry A
- Vol. 111 (38), 9326-9335
- https://doi.org/10.1021/jp0733466
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 Å 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.Keywords
This publication has 48 references indexed in Scilit:
- Photolysis of CBr4 and Its Transient Solvent Stabilized (CBr3+//Br-)Solv Ion PairThe Journal of Physical Chemistry A, 2005
- Simulation of x-ray absorption near edge spectra of electronically excited ruthenium tris-2,2′-bipyridineThe Journal of Chemical Physics, 2004
- Electronic Structure Contributions to Electron-Transfer Reactivity in Iron−Sulfur Active Sites: 3. Kinetics of Electron TransferInorganic Chemistry, 2003
- Thymine carboxylation: nucleophilic addition of carbon dioxide radical anionInternational Journal of Radiation Biology, 2000
- Dynamics of light-induced excited state quenching of ferrioxalate complexes by peroxides. Fast kinetics events and interaction with toxic pollutantsJournal of Photochemistry and Photobiology A: Chemistry, 1996
- The dependence on wavelength of 13C isotope effects in photolysis of aqueous solutions of ferrie oxalateCanadian Journal of Chemistry, 1976
- Spectrophotometric and electrochemical studies of flash-photolyzed trioxalatoferrate(III)The Journal of Physical Chemistry, 1973
- Oxidation of hypophosphorous acid by vanadium(V)The Journal of Physical Chemistry, 1971
- Pulse radiolysis of aliphatic acids in aqueous solutions. I. Simple monocarboxylic acidsThe Journal of Physical Chemistry, 1969
- CXCVII.—The photolysis of potassium ferrioxalate solutions. Part I. ExperimentalJournal of the Chemical Society, 1929