Reaction of an Ion and a Free Radical near 0 K: He +  + NO → He + N +  + O.

The reactions between ions and free radicals are among the fastest chemical reactions. They are predicted to proceed with large rates, even near 0 K, but so far, this prediction has not been verified experimentally. We report on measurements of the rate coefficient of the reaction between the ion He + and the free radical NO at collision energies in the range between 0 and ∼ k B ·10 K. To avoid heating of the ions by stray electric fields, the reaction is observed within the large orbit of a Rydberg electron of principal quantum number n ≥ 30, which shields the ion from external electric fields without affecting the reaction. Low collision energies are reached by merging a supersonic beam of He Rydberg atoms with a supersonic beam of NO molecules and adjusting their relative velocity using a chip-based Rydberg-Stark decelerator and deflector. We observe a strong enhancement of the reaction rate at collision energies below ∼ k B ·2 K. This enhancement is interpreted on the basis of adiabatic-channel capture-rate calculations as arising from the near-degenerate rotational levels of opposite parity resulting from the Λ-doubling in the X 2 Π 1/2 ground state of NO. With these new results, we examine the reliability of broadly used approximate analytic expressions for the thermal rate constants of ion-molecule reactions at low temperatures.