Unravelling the ultrafast photodecomposition mechanism of dibenzoyl peroxide in solution by time-resolved IR spectroscopy
Literature Information
Christian Reichardt, Peter Vöhringer, Dirk Schwarzer
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 13C-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 S1-lifetime of DBPO and within 0.4 ± 0.2 ps leads to a benzoyloxy/phenyl radical pair plus CO2via 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.
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DOI: 10.1039/B405513F
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.











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