%0 Journal Article %T First-Principles Chemical Kinetic Modeling of Methyl trans -3-Hexenoate Epoxidation by HO 2 %+ IFP Energies nouvelles (IFPEN) %+ Institut Carnot IFPEN Transports Energie %+ Argonne National Laboratory [Lemont] (ANL) %A Cagnina, Stefania %A Nicolle, André %A de Bruin, Theodorus %A Georgievskii, Youri %A Klippenstein, Stephen, J. %< avec comité de lecture %@ 1089-5639 %J Journal of Physical Chemistry A %I American Chemical Society %V 121 %N 9 %P 1909 - 1915 %8 2017-02-28 %D 2017 %R 10.1021/acs.jpca.7b00519 %Z Chemical SciencesJournal articles %X The design of innovative combustion processes relies on a comprehensive understanding of biodiesel oxidation kinetics. The present study aims at unraveling the reaction mechanism involved in the epoxidation of a realistic biodiesel surrogate, methyl trans-3-hexenoate, by hydroperoxy radicals using a bottom-up theoretical kinetics methodology. The obtained rate constants are in good agreement with experimental data for alkene epoxidation by HO2. The impact of temperature and pressure on epoxidation pathways involving H-bonded and non-H-bonded conformers was assessed. The obtained rate constant was finally implemented into a state-of-the-art detailed combustion mechanism, resulting in fairly good agreement with engine experiments. %G English %L hal-01760363 %U https://ifp.hal.science/hal-01760363 %~ IFP