Multipole-moment effects in ion-molecule reactions at low temperatures: part I -- Ion-dipole enhancement of the rate coefficients of the He$^+$ + NH$_3$ and He$^+$ + ND$_3$ reactions at collision energies near $0$ K

TL;DR

This study measures low-temperature ion-molecule reaction rates between He$^+$ and ammonia isotopologues, revealing a sharp increase below 5 K due to electric field effects and providing insights relevant for astrochemistry.

Contribution

It introduces a novel merged-beam technique with Rydberg atoms to accurately measure reaction rates at near-zero Kelvin, and interprets results with an adiabatic capture model accounting for electric field effects.

Findings

Reaction rates increase sharply below 5 K.

Deviations from Langevin-capture behavior observed.

Only 40% of close collisions are reactive at low temperatures.

Abstract

The energy dependence of the rates of the reactions between He$^+$ and ammonia (NY$_3$, Y= {H,D}), forming NY$_2^+$, Y and He as well as NY$^+$, Y$_2$ and He, and the corresponding product branching ratios have been measured at low collision energies between 0 and $k_{\mathrm{B}}\cdot40$ K using a recently developed merged-beam technique [Allmendinger {\it et al.}, ChemPhysChem {\bf 17}, 3596 (2016)]. To avoid heating of the ions by stray electric fields, the reactions are observed within the large orbit of a highly excited Rydberg electron. A beam of He Rydberg atoms was merged with a supersonic beam of ammonia using a curved surface-electrode Rydberg-Stark deflector, which was also used for adjusting the final velocity of the He Rydberg atoms, and thus the collision energy ($E_{\rm coll}$). A collision-energy resolution of about 200 mK was reached at the lowest $E_{\rm coll}$ values. The reaction rate coefficients exhibit a sharp increase at collision energies below $\sim k_{\mathrm{B}}\cdot5$ K and pronounced deviations from Langevin-capture behaviour. The experimental results are interpreted in terms of an adiabatic capture model describing the rotational-state-dependent orientation of the ammonia molecules by the electric field of the He$^+$ atom. The model faithfully describes the experimental observations. The enhancement of the reaction yields of both reactions observed at the lowest collision energies is attributed to high-field-seeking states which experience linear Stark shifts at low electric fields. Thermal capture rate constants are derived from the model for the temperature range between 0 and 10~K relevant for astrochemistry. Comparison of the calculated thermal capture rate coefficients with the absolute reaction rates measured above 27 K by Marquette {\it et al.} (Chem. Phys. Lett., 1985, {\bf 122}, 431) suggests that only 40\% of the close collisions are reactive.