Strong inverse kinetic isotope effect observed in ammonia charge exchange reactions

Abstract

AbstractIsotopic substitution has long been used to understand the detailed mechanisms of chemical reactions; normally the substitution of hydrogen by deuterium leads to a slower reaction. Here, we report our findings on the charge transfer collisions of cold $${{\rm{Xe}}}^{+}$$Xe+ ions and two isotopologues of ammonia, $${{\rm{NH}}}_{3}$$NH3 and $${{\rm{ND}}}_{3}$$ND3. Deuterated ammonia is found to react more than three times faster than hydrogenated ammonia. Classical capture models are unable to account for this pronounced inverse kinetic isotope effect. Moreover, detailed ab initio calculations cannot identify any (energetically accessible) crossing points between the reactant and product potential energy surfaces, indicating that electron transfer is likely to be slow. The higher reactivity of $${{\rm{ND}}}_{3}$$ND3 is attributed to the greater density of states (and therefore lifetime) of the deuterated reaction complex compared to the hydrogenated system. Our observations could provide valuable insight into possible mechanisms contributing to deuterium fractionation in the interstellar medium.