title: Theoretical Investigation of Intramolecular Hydrogen Shift Reactions in 3-Methyltetrahydrofuran (3-MTHF) Oxidation.
abstract: 3-Methyltetrahydrofuran (3-MTHF) is proposed to be a promising fuel component among the cyclic oxygenated species. To have detailed insight of its combustion kinetics, intramolecular hydrogen shift reactions for the ROO to QOOH reaction class are studied for eight ROO isomers of 3-MTHF. Rate constants of all possible reaction paths that involve formation of cyclic transition states are computed by employing the CBS-QB3 composite method. A Pitzer-Gwinn-like approximation has been applied for the internal rotations in reactants, products, and transition states for the accurate treatment of hindered rotors. Calculated relative barrier heights highlight that the most favorable reaction channel proceeds via a six membered transition state, which is consistent with the computed rate constants. Comparing total rate constants in ROO isomers of 3-MTHF with the corresponding isomers of methylcyclopentane depicts faster kinetics in 3-MTHF than methylcyclopentane reflecting the effect of ring oxygen on the intramolecular hydrogen shift reactions.
authors.affiliation: Physico Chemical Fundamentals of Combustion, RWTH Aachen University , Schinkelstraße 8, 52062 Aachen, Germany.
authors.forename: Prajakta R
authors.initials: PR
authors.lastname: Parab
authors.affiliation: Department of Mechanical Engineering, University of Fukui , Bunkyo 3-9-1, Fukui 9108507, Japan.
authors.forename: Naoki
authors.initials: N
authors.lastname: Sakade
authors.affiliation: Department of Mechanical Engineering, University of Fukui , Bunkyo 3-9-1, Fukui 9108507, Japan.
authors.forename: Yasuyuki
authors.initials: Y
authors.lastname: Sakai
authors.affiliation: Physikalisch Technische Bundesanstalt (PTB) Bundesallee 100, 38116 Braunschweig, Germany.
authors.forename: Ravi
authors.initials: R
authors.lastname: Fernandes
authors.affiliation: Physico Chemical Fundamentals of Combustion, RWTH Aachen University , Schinkelstraße 8, 52062 Aachen, Germany.
authors.forename: K Alexander
authors.initials: KA
authors.lastname: Heufer