Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 5, Issue 23, Pages 4213-4218Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jz502236y
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Funding
- MIUR (PRIN) [2010ERFKXL]
- EC COST Action [CM0901]
- Fondazione Cassa di Risparmio di Perugia (Codice Progetto: Ricerca Scientifica e Tecnologica) [2014.0253.021]
- ESF Competitiveness and Employment objective Umbrian Regional Operational Programme (ROP) through a postdoc grant
- bilateral project UIF/UFI - Galileo Project [G12-70]
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Comprehension of the detailed mechanism of O(P-3) + unsaturated hydrocarbon reactions is complicated by the existence of many possible channels and intersystem crossing (ISC) between triplet and singlet potential energy surfaces (PESs). We report synergic experimental/theoretical studies of the O(P-3) + propene reaction by combining crossed molecular beams experiments using mass spectrometric detection at 9.3 kcal/mol collision energy (E-c) with high-level ab initio electronic structure calculations of the triplet PES and RRKM/master equation computations of branching ratios (BRs) including ISC. At high E-c's and temperatures higher than 1000 K, main products are found to be formaldehyde (H2CO) and triplet ethylidene ((CH3CH)-C-3) formed in a reaction channel that has never been identified or considered significant in previous kinetics studies at 300 K and that, as such, is not included in combustion kinetics models. Global and channel-specific rate constants were computed and are reported as a function of temperature and pressure. This study shows that BRs of multichannel reactions useful for combustion modeling cannot be extrapolated from room-temperature kinetics studies.
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