DOE OSTI2024
We have achieved the proposed goal to experimentally probe the AB + CD and AB + C types of reactions with state-to-state resolution, which we also compared to advanced theoretical calculations to help elucidate the role of quantum mechanics in the processes of bond breakage and formation. Our approach uses reactants that are prepared at ultracold temperatures (< 1µK) such that the quantum effects of translational motion are an important factor. Specific example reactions, including the potassium-rubidium metathesis reaction KRb + KRb → K 2 + Rb 2 as well as the atom exchange reaction Rb + KRb → Rb2 + K, are chosen because the technology of quantum internal and motional state control of these types of molecules is particularly advanced. The results for the entire funding period are fruitful. For the majority of this grant, we have constructed a one-of-the-kind quantum degenerate gas apparatus that integrates ion detection and velocity map imaging capabilities, allowing us to explore the KRb + KRb → K 2 + Rb 2 bimolecular reaction in detail. Specifically, we first verified such a reaction indeed proceed at ultracold temperatures by direct detection of reaction products. We then mapped out the complete product state distribution, which was compared to a state-counting model based on statistical theory. Our results show an overall agreement with the statistical state counting model, but also reveal several deviating state-pairs. An exact quantum calculation for molecule-molecule collisions, that is needed to understand these deviations, is however beyond the current state-of-the-art. Beside scrutinizing the reaction products, we also directly observe the reaction intermediate complex, which was quite a surprise to us. The intermediate complexes are long-lived and can interact with the inferred light that we use to trap the ultracold gas. After molecule-molecule collisions, we then explored the more theoretically tractable Rb + KRb reaction, which is endothermic. Surprisingly, we observed an exceedingly long-lived KRb$^*_2$ collisional complexes, with our experimentally measured complex lifetime deviating from conventional theoretical calculations by five orders of magnitude. This discrepancy has motivated many explorations of possible underlying causes, though no model yet captures this phenomenon completely. In the final year and the work that continues today, we extend upon these atom-molecule collision experiments to explore the origin of the long-lived KRb$^*_2$ complex lifetime and develop means to control the outcome of the reaction complex. The 5-year funded work advanced our understanding of chemical reactions at the lowest possible temperatures and at the same time opened up many new questions that are beyond our initial imaginations.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗