Three-Body Collisions Driving the Ion–Molecule Reaction C₂^– + H₂ at Low Temperatures

Abstract

We report on the three-body reaction rate of C2 – with H2 producing C2H– studied in a cryogenic 16-pole radio frequency ion trap. The reaction was measured in the temperature range from 10 to 28 K, where it was found to only take place via three-body collisions. The experimentally determined termolecular rate coefficient follows the form of a · ( T / T 0 ) b with T 0 = 20 K, where a = 8.2(3) × 10–30 cm6/s and b = −0.82(12) denotes the temperature dependence. We additionally performed accurate ab initio calculations of the forces between the interacting partners and carried out variational transition state theory calculations, including tunneling through the barrier along the minimum energy path. We show that, while a simple classical model can generally predict the temperature dependence, the variational transition state theoretical calculations, including accurate quantum interactions, can explain the dominance of three-body effects in the molecular reaction mechanism and can reproduce the experimentally determined reaction coefficients, linking them to a temperature-dependent coupling parameter for energy dissipation within the transition complex.

Cold Chemistry

“…Lochman et al. use an ion trap to probe the otherwise elusive three-body reaction rate that produces C 2 H – from stabilization of a C 2 H 2 – complex, produced in C 2 – + H 2 collisions, upon encountering a second H 2 molecule . Variational transition state theory accounts admirably for the results, by identifying the primary reaction path barrier.…”