Isomerization and decomposition of a Criegee intermediate in the ozonolysis of alkenes: dynamics using a multireference potential

التفاصيل البيبلوغرافية
العنوان: Isomerization and decomposition of a Criegee intermediate in the ozonolysis of alkenes: dynamics using a multireference potential
المؤلفون: Petri Heinonen, Markku Räsänen, Ilkka Kilpeläinen, Jaroslaw Kalinowski, R. Benny Gerber
المصدر: Angewandte Chemie (International ed. in English). 53(1)
سنة النشر: 2013
مصطلحات موضوعية: Ozonolysis, Diradical, Chemistry, General Chemistry, General Medicine, Catalysis, Transition state, chemistry.chemical_compound, Molecular dynamics, Dioxirane, Computational chemistry, Ab initio quantum chemistry methods, Criegee intermediate, Isomerization
الوصف: The isomerization and decomposition dynamics of the simplest Criegee intermediate CH2 OO have been studied by classical trajectory simulations using the multireference ab initio MR-PT2 potential on the fly. A new, accelerated algorithm for dynamics with MR-PT2 was used. For an initial temperature of 300 K, starting from the transition state from CH2 OO→CH2 O2 , the system reaches the dioxirane structure in around 50 fs, then isomerizes to formic acid (in ca. 2800 fs), and decomposes into CO+H2 O at around 2900 fs. The contributions of different configurations to the multiconfigurational total electronic wave function vary dramatically along the trajectory, with diradical contributions being important for transition states corresponding to H-atom transfers, while being only moderately significant for CH2 OO. The implications for reactions of Criegee intermediates are discussed.
تدمد: 1521-3773
URL الوصول: https://explore.openaire.eu/search/publication?articleId=doi_dedup___::bdb9a94766ce180a4c0dd50f5820a14f
https://pubmed.ncbi.nlm.nih.gov/24227050
Rights: CLOSED
رقم الانضمام: edsair.doi.dedup.....bdb9a94766ce180a4c0dd50f5820a14f
قاعدة البيانات: OpenAIRE