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Femtosecond infrared spectroscopy of aroylperoxide photofragmentation – Site selective decarboxylation.

MPS-Authors
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Vennekate,  H.
Department of Dynamics at Surfaces, MPI for Biophysical Chemistry, Max Planck Society;

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Walter,  A.
Emeritus Group of Spectroscopy and Photochemical Kinetics, MPI for Biophysical Chemistry, Max Planck Society;

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Fuest,  H.
Research Group of Structural Dynamics of (Bio)Chemical Systems, MPI for biophysical chemistry, Max Planck Society;

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Schroeder,  J.
Emeritus Group of Spectroscopy and Photochemical Kinetics, MPI for Biophysical Chemistry, Max Planck Society;

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Schwarzer,  D.
Department of Dynamics at Surfaces, MPI for Biophysical Chemistry, Max Planck Society;

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Citation

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.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0029-1D3E-A
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.