Hierarchical study of the reactions of hydrogen atoms with alkenes: A theoretical study of the reactions of hydrogen atoms with C2–C4 alkenes
Somers, Kieran P.
Nagaraja, Shashank S.
Curran, Henry J.
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Power, Jennifer, Somers, Kieran P., Nagaraja, Shashank S., & Curran, Henry J. (2021). Hierarchical Study of the Reactions of Hydrogen Atoms with Alkenes: A Theoretical Study of the Reactions of Hydrogen Atoms with C2–C4 Alkenes. The Journal of Physical Chemistry A, 125(23), 5124-5145. doi: 10.1021/acs.jpca.1c03168
The present study complements our previous studies of the reactions of hydrogen atoms with C5 alkene species including 1- and 2-pentene and the branched isomers (2-methyl-1-butene, 2-methyl-2-butene, and 3-methyl-1-butene), by studying the reactions of hydrogen atoms with C2¿C4 alkenes (ethylene, propene, 1- and 2-butene, and isobutene). The aim of the current work is to develop a hierarchical set of rate constants for ¿ atom addition reactions to C2¿C5 alkenes, both linear and branched, which can be used in the development of chemical kinetic models. High-pressure limiting and pressure-dependent rate constants are calculated using the Rice¿Ramsperger¿Kassel¿Marcus (RRKM) theory and a one-dimensional master equation (ME). Rate constant recommendations for ¿ atom addition and abstraction reactions in addition to alkyl radical decomposition reactions are also proposed and provide a useful tool for use in mechanisms of larger alkenes for which calculations do not exist. Additionally, validation of our theoretical results with single-pulse shock-tube pyrolysis experiments is carried out. An improvement in species mole fraction predictions for alkene pyrolysis is observed, showing the relevance of the present study.