Ion-molecule reactions involving HCO$^+$ and N$_2$H$^+$: Isotopologue equilibria from new theoretical calculations and consequences for interstellar isotope fractionation

TL;DR

This study uses advanced theoretical methods to refine the understanding of isotope exchange reactions involving HCO$^+$ and N$_2$H$^+$, revealing new energetics and abundance ratios crucial for interstellar chemistry models.

Contribution

The paper introduces new high-accuracy calculations of isotope exchange reactions, providing updated rate coefficients and insights into the stability of proton-bound complexes in interstellar environments.

Findings

New exothermicities for HCO$^+$ + CO reactions alter predicted isotope ratios.

Reaction pathways involve stable proton-bound complexes with significant dipole moments.

Updated abundance ratios impact models of interstellar isotope fractionation.

Abstract

$Aims$: We revisit with new augmented accuracy the theoretical dynamics of basic isotope exchange reactions involved in the $^{12}$C/$^{13}$C, $^{16}$O/$^{18}$O, and $^{14}$N/$^{15}$N balance because these reactions have already been studied experimentally in great detail. $Methods$: Electronic structure methods were employed to explore potential energy surfaces, full-dimensional rovibrational calculations to compute rovibrational energy levels that are numerically exact, and chemical network models to estimate the abundance ratios under interstellar conditions. $Results$: New exothermicities, derived for HCO$^+$ reacting with CO, provide rate coefficients markedly different from previous theoretical values in particular at low temperatures, resulting in new abundance ratios relevant for carbon chemistry networks. In concrete terms, we obtain a reduction in the abundance of H$^{12}$C$^{18}$O$^+$ and an increase in the abundance of H$^{13}$C$^{16}$O$^+$ and D$^{13}$C$^{16}$O$^+$. In all studied cases, the reaction of the ion with a neutral polarizable molecule proceeds through the intermediate proton-bound complex found to be very stable. For the complexes OCH$^+$...CO, OCH$^+$...OC, COHOC$^+$, N$_2$...HCO$^+$, N$_2$H$^+$...OC, and N$_2$HN$_2^+$, we also calculated vibrational frequencies and dissociation energies. $Conclusions$: The linear proton-bound complexes possess sizeable dipole moments, which may facilitate their detection.