Dynamics of gas phase Ne$^*$ + NH$_3$ and Ne$^*$ + ND$_3$ Penning ionization at low temperatures

TL;DR

This study investigates low-temperature Penning ionization of NH3 and ND3 by Ne* using merged beams, revealing energy-dependent cross sections, the inadequacy of the Langevin model, and insights from quantum defect theory.

Contribution

It provides the first detailed experimental and theoretical analysis of Ne* + NH3 and ND3 reactions at low energies, highlighting the role of long-range interactions and reaction dynamics.

Findings

Cross sections increase as collision energy decreases.

Langevin model does not fully describe the reactions.

Quantum defect theory matches experimental data well.

Abstract

Two isotopic chemical reactions, $\mathrm{Ne}^*$ + NH$_3$, and $\mathrm{Ne}^*$ + ND$_3$, have been studied at low collision energies by means of a merged beams technique. Partial cross sections have been recorded for the two reactive channels, namely $\mathrm{Ne}^*$ + NH$_3$ $\rightarrow$ Ne + NH$_3^+$ + $e^-$, and $\mathrm{Ne}^*$ + NH$_3$ $\rightarrow$ Ne + NH$_2^+$ + H + $e^-$, by detecting the NH$_3^+$ and NH$_2^+$ product ions, respectively. The cross sections for both reactions were found to increase with decreasing collision energy, $E_{coll}$, in the range 8 $\mu$eV$<E_{coll}<$ 20 meV. The measured rate constant exhibits a curvature in a log(k)-log($E_{coll}$) plot from which it is concluded that the Langevin capture model does not properly describe the $\mathrm{Ne}^*$ + NH$_3$ reaction in the entire range of collision energies covered here. Calculations based on multichannel quantum defect theory were performed to reproduce and interpret the experimental results. Good agreement was obtained by including long range van der Waals interactions combined with a 6-12 Lennard-Jones potential. The branching ratio between the two reactive channels, $\Gamma = \frac{[NH_2^+]}{[NH_2^+]+[NH_3^+]}$, is relatively constant, $\Gamma\approx 0.3$, in the entire collision energy range studied here. Possible reasons for this observation are discussed and rationalised in terms of relative time scales of the reactant approach and the molecular rotation. Isotopic differences between the $\mathrm{Ne}^*$ + NH$_3$ and $\mathrm{Ne}^*$ + ND$_3$ reactions are small, as suggested by nearly equal branching ratios and cross sections for the two reactions.