Mechanistic Insights into Ultracold Chemical Reactions under the Control of the Geometric Phase

Ultracold chemical reactions involve collision temperatures approaching absolute zero, and for molecular systems that exhibit a barrierless and exoergic reaction path significant reactivity can occur. In addition, many molecules contain a conical intersection, and the associated geometric phase has been shown to significantly alter the outcome of ultracold reactions. Here we report a quantum dynamics study for the ultracold O + OH → H + O₂ reaction. An analysis of the scattering wave functions reveals explicitly the nature of the quantum interference between the direct and looping reaction pathways around the conical intersection and thus illustrates how the reaction proceeds under the control of the geometric phase for the first time. The wave function analysis should generalize to other ultracold reactions that contain a conical intersection. Our findings indicate that quantum control techniques such as an optical lattice trap or the initial state orientation may be effective in controlling the reactivity.