Direct dynamics in a proton transfer reaction of isomer product competition. Insight into the suppressed formation of the isoformyl cation

Abstract

Proton transfer between HOCO⁺ and CO produces the formyl cation HCO⁺ and isoformyl cation HOC⁺ isomers initiating multiple astrochemical reaction networks. Here, the direct chemical dynamics simulations are performed to uncover the underlying atomistic dynamics of the above reaction. The simulations reproduce the measured product energy and scattering angle distributions and reveal that the reaction proceeds predominantly through a direct stripping mechanism which results in the prominent forward scattering observed in experiments. The reaction dynamics show propensity for the HCO⁺ product even at a collision energy larger than the threshold for HOC⁺ formation. This is a consequence of the larger opacity and impact parameter range for HCO⁺. In accordance with the revealed direct mechanistic feature, the reaction can be controlled by orienting the reactants into a reactive H–C orientation that also favors HCO⁺ formation. Considering the lack of equilibrated reactant complexes and the on the fly migration of the proton, the CO₂-catalyzed isomerization is assumed to have insignificant impact on the isomer ratios. This work provides insights of dynamical effects besides energetics into the interesting finding of strongly suppressed formation of the metastable isoformyl cation for related proton transfer reactions in the measurements.