Isomer-resolved ion-molecule reaction kinetics of HCO+ and HOC+

The HCO${}^{+}$/HOC${}^{+}$ abundance ratio has been observed to vary significantly in different astrophysical environments, making it an important diagnostic tool for exploring the interstellar medium. However, uncertainties in the reaction rates and branching ratios of key chemical reactions involving these ions affect the conclusions drawn from observations of either these species or other species that are derived on their basis. Here, we present isomer-resolved ion-molecule reaction rate coefficients of reactions involving HCO${}^{+}$ and HOC${}^{+}$ using a cryogenic ion trap experiment. We measured the rate coefficients of the isomerization reaction of HOC${}^{+}$ to HCO${}^{+}$ with H${}_2$ and CO, as well as three different reactions producing both isomers: CO${}^{+}$ + H${}_2$ , H${}_3^{+}$ + CO, and ArH${}^{+}$ + CO. Our results show that the reaction of CO${}^{+}$ with H${}_2$ predominantly produces HCO${}^{+}$ with a negligible yield of HOC${}^{+}$ . This result is in agreement with recent theoretical predictions, but in major contrast to the generally accepted branching ratio based on previous experimental results. We also find that the isomerization reaction of HOC${}^{+}$ to HCO${}^{+}$ is efficient with both H2 and CO. We were able to assess the impact of our new measured reaction rate coefficients on the predicted HCO${}^{+}$/HOC${}^{+}$ abundance ratio using a state-of-the-art astrochemical model.