Pulse radiolytic studies of electron transfer processes and applications to solar photochemistry. Progress report
The pulse radiolysis technique is applied to the study of electron transfer processes in a variety of chemical systems. Reactive intermediates are produced in solution by electron pulse irradiation and the kinetics of their reactions are followed by time resolved absorption spectrophotometry. Complementary experiments are carried out with excimer laser flash photolysis. These studies are concerned with mechanisms, kinetics, and thermodynamics of reactions of organic and inorganic radicals and unstable oxidation states of metal ions. Reactions are studied in both aqueous and non-aqueous solutions. The studies focus on the unique ability of pulse radiolysis to provide absolute rate constants for reactions of many inorganic radicals and organic peroxyl radicals, species that are key intermediates in many chemical processes. A special concern of this work is the study of electron transfer reactions of metalloporphyrins, which permits evaluation of these molecules as intermediates in solar energy conversion. Metalloporphyrins react with free radicals via electron transfer, involving the ligand or the metal center, or via bonding to the metal, leading to a variety of chemical species whose behavior is also investigated. The highlights of the results during the past three years are summarized below under the following sections: (a) electron transfer reactions of peroxyl radicals, concentrating on the characterization of new peroxyl radicals derived from vinyl, phenyl, other aryl, and pyridyl; (b) solvent effects on electron transfer reactions of inorganic and organic peroxyl radicals, including reactions with porphyrins, and (c) electron transfer and alkylation reactions of metalloporphyrins and other complexes.
- Research Organization:
- National Inst. of Standards and Technology, Gaithersburg, MD (United States)
- Sponsoring Organization:
- USDOE Office of Energy Research, Washington, DC (United States)
- DOE Contract Number:
- AI05-83ER13108
- OSTI ID:
- 584884
- Report Number(s):
- DOE/ER/13108--T9; ON: DE98004348
- Country of Publication:
- United States
- Language:
- English
Similar Records
Pulse radiolytic studies of electron transfer processes and applications to solar photochemistry
Pulse radiolytic studies of electron transfer processes and applications to solar photochemistry
Pulse radiolytic studies of electron transfer processes and applications to solar photochemistry. [Final] progress report, [February 1989--January 1992]
Technical Report
·
Thu Jan 16 23:00:00 EST 1992
·
OSTI ID:6287398
Pulse radiolytic studies of electron transfer processes and applications to solar photochemistry
Technical Report
·
Fri Apr 20 00:00:00 EDT 1990
·
OSTI ID:6158267
Pulse radiolytic studies of electron transfer processes and applications to solar photochemistry. [Final] progress report, [February 1989--January 1992]
Technical Report
·
Thu Jan 16 23:00:00 EST 1992
·
OSTI ID:10169533