title: Reactions of Chemically Activated Formic Acid Formed via HĊO + ȮH.
abstract: The chemistry of formyl radicals plays an important role in the kinetic modeling of oxygenated hydrocarbons. Here, the fate of rovibrationally excited formic acid produced via HĊO + ȮH is evaluated in a RRKM/Master Equation study. For that purpose, the HĊO + ȮH potential energy surface is studied theoretically using high-level quantum mechanics. Direct reaction from HĊO + ȮH to the bimolecular products is found to dominate for most relevant conditions due to formic acid well-skipping. The kinetics of these well-skipping reactions can only be evaluated when including the unimolecular intermediate, formic acid. Further, hydrogen abstraction from rovibrationally excited formic acid is found to be important at low-temperature conditions and for high radical concentrations.
authors.affiliation: Chair of Technical Thermodynamics, and ‡AICES Graduate School, RWTH Aachen University , Aachen, 52062, Germany.
authors.forename: Malte
authors.initials: M
authors.lastname: Döntgen
authors.affiliation: Chair of Technical Thermodynamics, and ‡AICES Graduate School, RWTH Aachen University , Aachen, 52062, Germany.
authors.forename: Kai
authors.initials: K
authors.lastname: Leonhard