Reactions of Chemically Activated Formic Acid Formed via HĊO + ȮH

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.