Photo-induced decomposition of organic peroxides: Ultrafast formation and decarboxylation of carbonyloxy radicals
Literature Information
Michael Buback, Matthias Kling, Stefan Schmatz, Jörg Schroeder
Recent experimental and theoretical studies shed new light on the ultrafast photochemical decomposition of organic peroxides, R1C(O)O–OR2. This reaction both is of fundamental interest, directed toward a detailed understanding of unimolecular processes, and of practical relevance because of the widespread use of peroxides as initiators in free-radical polymerization. An overview is given on pico- and femtosecond UV pump-VIS/near IR/IR probe experiments on the decomposition of diaroyl peroxides (R1 = aryl, R2 = C(O)–R1), of tert-butyl peroxyesters (R1 = aryl or benzyl, R2 = tert-butyl), and of tert-butyl peroxycarbonates (R1 = aryloxy, R2 = tert-butyl). Analysis of the time-resolved concentration profiles is carried out in conjunction with quantum-chemical calculations, in particular on the structure and reactivity of the intermediate carbonyloxy radicals, R1–CO2. A semi-quantitative model is presented which allows for an adequate understanding of the ultrafast processes subsequent to instantaneous peroxide photodissociation.
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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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