Ni, Kang-KuenZhu, Lingbang2026-01-1520252025-09-052025Zhu, Lingbang. 2025. Ultracold Atom-Polar Molecule Interactions: Discoveries, Surprises and Puzzles. Doctoral Dissertation, Harvard University Graduate School of Arts and Sciences.32241060https://dash.harvard.edu/handle/1/42725552Studying ultracold chemical reactions with quantum state resolution reveals details of the reaction processes, especially with single quantum state preparation of the reactants and state-selective detection of reaction products. In this thesis, we investigate two main processes: KRb + KRb → K2 + Rb2 reactions, and Rb and KRb atom-molecule collisions. In the KRb bimolecular reaction, we demonstrate the preservation of quantum coherence in bimolecular reactions for the first time, which is surprising in a reaction considered to be largely chaotic. Additionally, we proposed a coherent control scheme to manipulate product yields across different product channels. These results represent a critical step toward probing quantum coherence and entanglement in the chemical reaction. In atom-molecule collisions between Rb and KRb, we discovered an exceptionally long-lived intermediate complex, KRb2, which can be photo-excited by trapping light. The observed complex lifetime was orders of magnitude longer than theoretical predictions, underscoring the limitations of the current theory. We further explored the dependence of complex lifetimes on the initial quantum states and external electric and magnetic fields, providing additional experimental benchmarks to guide future theoretical work. Separately, we found that inelastic collisions between hyperfine-excited Rb atoms and KRb molecules can lead to rotation excitation of KRb post-collision. By probing the product state distribution, the result suggests that mechanical angular momentum is coupled to the spins. Such couplings are too weak in the current theory models to explain the result. Moreover, our result contradicts state-of-the-art coupled-channel calculations. These suggest that some subtle effects, such as molecular vibration and conical intersections, play a critical role in the reaction dynamics. The final piece of the thesis describes the observation of resonant interaction between a Rydberg atom and an ensemble of polar molecules. Such hybrid quantum systems have been proposed for a wide range of applications. Our work provides an experimental demonstration of resonant dipolar interactions between Rydberg atoms and ultracold polar molecules, paving the way for the realization of hybrid systems for quantum computation and simulation.application/pdfenDipolar interactionQuantum entanglementQuantum interferenceUltracold chemistryUltracold moleculesPhysical chemistryAtomic physicsQuantum physicsThesis or Dissertation2026-01-150009-0005-6836-2010