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

We report on the three-body reaction rate of C-2- with H-2 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 center dot(T/T)b 0 with T0 = 20 K, where a = 8.2(3) x 10(-30) cm(6)/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.

Automated summary

We report the three-body reaction rate of C-2- with H-2 producing C2H- measured in a cryogenic ion trap. The experimentally determined termolecular rate coefficient follows a temperature dependence of center dot(T/T)b 0 with T0 = 20 K. Accurate ab initio calculations and variational transition state theory calculations were performed to explain the dominance of three-body effects in the reaction mechanism and reproduce the experimentally determined reaction coefficients.