Unravelling the ultrafast photodecomposition mechanism of dibenzoyl peroxide in solution by time-resolved IR spectroscopy
2008 | journal article. A publication with affiliation to the University of Göttingen.
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Unravelling the ultrafast photodecomposition mechanism of dibenzoyl peroxide in solution by time-resolved IR spectroscopy
Reichardt, C.; Schroeder, J.; Voehringer, P. & Schwarzer, D. (2008)
Physical Chemistry Chemical Physics, 10(12) pp. 1662-1668. DOI: https://doi.org/10.1039/b718501d
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Details
- Authors
- Reichardt, Christian; Schroeder, Joerg; Voehringer, Peter; Schwarzer, Dirk
- Abstract
- The ultrafast photo-fragmentation of dibenzoyl peroxide (DBPO) is studied using femtosecond UV excitation at 266 nm and mid-infrared broadband probe pulses to elucidate the dissociation mechanism. With the help of C-13-labeled DBPO it was possible to unambiguously assign transient IR bands in the fingerprint region to the benzoyloxy radical. Our experiments show that the fragmentation is controlled by the S-1-lifetime of DBPO and within 0.4 +/- 0.2 ps leads to a benzoyloxy/phenyl radical pair plus CO2 via concerted bond breakage of the O-O and the phenyl-C(carbonyl) bond. 20% of the radical pairs geminately recombine to phenyl benzoate on a timescale of 70 ps.
- Issue Date
- 2008
- Status
- published
- Publisher
- Royal Soc Chemistry
- Journal
- Physical Chemistry Chemical Physics
- ISSN
- 1463-9076