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  Femtosecond infrared spectroscopy of aroylperoxide photofragmentation – Site selective decarboxylation.

Vennekate, H., Reichardt, C., Walter, A., Fuest, H., Schroeder, J., & Schwarzer, D. (2015). Femtosecond infrared spectroscopy of aroylperoxide photofragmentation – Site selective decarboxylation. Zeitschrift für Physikalische Chemie, 229(10-12), 1799-1814. doi:10.1515/zpch-2015-0629.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0029-1D3E-A Version Permalink: http://hdl.handle.net/11858/00-001M-0000-002A-F6CF-F
Genre: Journal Article

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 Creators:
Vennekate, H.1, Author              
Reichardt, C., Author
Walter, A.2, Author              
Fuest, H.3, Author              
Schroeder, J.2, Author              
Schwarzer, D.1, Author              
Affiliations:
1Department of Dynamics at Surfaces, MPI for Biophysical Chemistry, Max Planck Society, ou_578600              
2Emeritus Group of Spectroscopy and Photochemical Kinetics, MPI for Biophysical Chemistry, Max Planck Society, ou_578625              
3Research Group of Structural Dynamics of (Bio)Chemical Systems, MPI for biophysical chemistry, Max Planck Society, ou_578564              

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Free keywords: Reaction dynamics; Photochemistry; Femtosecond IR spectroscopy
 Abstract: The ultrafast photofragmentation of acetyl-benzoyl peroxide (ABPO) and 2-naphthoyl-benzoyl peroxide (NBPO) after UV excitation at 266 nm is studied by mid-infrared transient absorption spectroscopy. 13C-isotopic labelling is employed to unravel the primary fragmentation paths. For NBPO it appears that excitation of the benzoyloxy part causes decarboxylation exclusively at that site. In ABPO the acetyloxy part completely decarboxylates upon 266 nm excitation while only 80% – 85% of the benzoyloxyl radicals formed decarboxylate. The remaining radicals either combine with methyl radicals to methylbenzoate within about 30 ps or survive on the time scale of the experiment (1.5 ns). Photofragmentation of ABPO occurs from the S1-state whose lifetime is about 200 fs. All fragmentation products including CO2 also appear on this time scale.

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Language(s): eng - English
 Dates: 2015-07-102015-10
 Publication Status: Published in print
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 Rev. Method: Peer
 Identifiers: DOI: 10.1515/zpch-2015-0629
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Title: Zeitschrift für Physikalische Chemie
Source Genre: Journal
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Pages: - Volume / Issue: 229 (10-12) Sequence Number: - Start / End Page: 1799 - 1814 Identifier: -