Three-Body Collisions Driving the Ion–Molecule Reaction C(2)(–) + H(2) at Low Temperatures

[Image: see text] We report on the three-body reaction rate of C(2)(–) with H(2) producing C(2)H(–) 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 [Image: see text] with T(0) = 20 K, where a = 8.2(3) × 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.