Abstract Quantum effects in chemical reactions are most pronounced at ultracold temperatures, where only a few partial waves contribute. While interference among many partial waves is theoretically expected to persist at higher temperatures, direct evidence for such quantum effects in reactive processes has been lacking. Here, we report signatures of quantum interference suppressing a chemical reaction in the multi-partial-wave regime: resonant charge exchange between a single 87 Rb + ion and its parent atom 87 Rb. Using quantum-logic detection on a single atom-ion pair and a calibrated in-situ measurement of Langevin collision probabilities, we benchmark the thermally averaged reaction rate against both classical and quantum predictions. We find that the reaction rate is suppressed by over an order of magnitude relative to the classical expectation, despite occurring in the millikelvin temperature regime (more than three orders of magnitude above the s -wave threshold), where more than a dozen partial waves contribute. These results suggest quantum interference as a key mechanism in chemical reactivity beyond the ultracold limit and offer a platform for probing coherent quantum effects in atom-ion reactions where ab initio methods remain intractable.
Abstract Quantum effects in chemical reactions are most pronounced at ultracold temperatures, where only a few partial waves contribute. While interference among many partial waves is theoretically expected to persist at higher temperatures, direct evidence for such quantum effects in reactive processes has been lacking. Here, we report signatures of quantum interference suppressing a chemical reaction in the multi-partial-wave regime: resonant charge exchange between a single 87 Rb + ion and its parent atom 87 Rb. Using quantum-logic detection on a single atom-ion pair and a calibrated in-situ measurement of Langevin collision probabilities, we benchmark the thermally averaged reaction rate against both classical and quantum predictions. We find that the reaction rate is suppressed by over an order of magnitude relative to the classical expectation, despite occurring in the millikelvin temperature regime (more than three orders of magnitude above the s -wave threshold), where more than a dozen partial waves contribute. These results suggest quantum interference as a key mechanism in chemical reactivity beyond the ultracold limit and offer a platform for probing coherent quantum effects in atom-ion reactions where ab initio methods remain intractable.
Tunable scattering resonances are crucial for controlling atomic and molecular systems. However, their use has so far been limited to ultracold temperatures. These conditions remain hard to achieve for most hybrid trapped ion-atom systems—a prospective platform for quantum technologies and fundamental research. Here, we measure inelastic collision probabilities for Sr + + Rb and use them to calibrate a comprehensive theoretical model of ion-atom collisions. Our theoretical results, compared with experimental observations, confirm that quantum interference effects persist to the multiple-partial-wave regime, leading to the pronounced state and mass dependence of the collision rates. Using our model, we go beyond interference and identify a rich spectrum of Feshbach resonances at moderate magnetic fields with the Rb atom in its lower ( f = 1) hyperfine state, which persist at temperatures as high as 1 millikelvin. Future observation of these predicted resonances should allow precise control of the short-range dynamics in Sr + + Rb collisions under unprecedentedly warm conditions.
How does a chemical reaction proceed at ultralow temperatures? Can simple quantum mechanical rules such as quantum statistics, single partial-wave scattering, and quantum threshold laws provide a clear understanding of the molecular reactivity under a vanishing collision energy? Starting with an optically trapped near-quantum-degenerate gas of polar 40K87Rb molecules prepared in their absolute ground state, we report experimental evidence for exothermic atom-exchange chemical reactions. When these fermionic molecules were prepared in a single quantum state at a temperature of a few hundred nanokelvin, we observed p-wave-dominated quantum threshold collisions arising from tunneling through an angular momentum barrier followed by a short-range chemical reaction with a probability near unity. When these molecules were prepared in two different internal states or when molecules and atoms were brought together, the reaction rates were enhanced by a factor of 10 to 100 as a result of s-wave scattering, which does not have a centrifugal barrier. The measured rates agree with predicted universal loss rates related to the two-body van der Waals length.
Quantum interference in cold collisions has been predicted to dominate chemical dynamics at low temperatures. However, experimental observations have been largely confined to light-atom systems due to technical challenges. Here, we report direct observation of scattering oscillations in cold ionizing collisions between metastable krypton and rubidium atoms. By combining laser cooling with velocity-mapped ion imaging, we precisely controlled the collision energy from 15 millikelvin to 8 kelvin and detected the ionization products. Below 1 kelvin, pronounced quantum interference between partial waves emerges as the de Broglie wavelength approaches the interaction range. The angular oscillation period scales as [Formula: see text], consistent with a Langevin capture model for van der Waals-dominated collisions. Moreover, interference patterns in the angular distribution-collision temperature spectrum are highly sensitive to the long-range potential shape and reveal subtle shape resonances. These observations were corroborated by theoretical calculations. Our results demonstrate the quantum-classical crossover in heavy-atom systems. This study establishes a versatile platform for studying a wide range of laser-coolable species.
Studying chemical reactions at very low temperatures is of importance for the understanding of fundamental physical and chemical processes. At very low energies, collisions are dominated by only a few partial waves. Thus, studies in this regime allow the characterization of quantum effects which depend on the collisional angular momentum, e.g., reactive scattering resonances and tunneling through centrifugal barriers. Additionally, the dynamics of ultralow-energy collisions is dominated by long-range interactions, i.e., “universal” chemical forces. Thus, experiments in this domain probe the details of intermolecular interactions which is of general relevance for the understanding of chemical processes. Moreover, the increasingly more precise experiments provide valuable data for benchmarking theoretical models and quantum chemical calculations. Studies of cold ion–neutral reactions in the laboratory rely on techniques for the generation of cold ions and cold neutrals. Over the last decades, the technology in this domain has made impressive progress. Many of these techniques allow not only the translational cooling of the molecules, but also a precise preparation of their internal quantum state. Thus, by an accurate preparation of both the energy and state of the reaction partners as well as by the application of external electric, magnetic or optical fields, prospects open up to study and control chemical processes at an unprecedented level of accuracy. In this chapter, we review salient theoretical concepts and recent experimental developments for studies of ion–molecule reactions at low temperatures. We first discuss the theoretical background for the description of low-energy ion–molecule reactions. Next we present key experimental methods for laboratory studies of cold ion–molecule reactions. The chapter concludes with a review of illustrative results and an outlook on future directions.
Studying chemical reactions at very low temperatures is of importance for the understanding of fundamental physical and chemical processes. At very low energies, collisions are dominated by only a few partial waves. Thus, studies in this regime allow the characterisation of quantum effects which depend on the collisional angular momentum, e.g., reactive scattering resonances and tunneling through centrifugal barriers. Additionally, the dynamics of ultralow-energy collisions is dominated by long-range interactions, i.e., "universal" chemical forces. Thus, experiments in this domain probe the details of intermolecular interactions which is of general relevance for the understanding of chemical processes. Moreover, the increasingly more precise experiments provide valuable data for benchmarking theoretical models and quantum-chemical calculations. Studies of cold ion-neutral reactions in the laboratory rely on techniques for the generation of cold ions and cold neutrals. Many of these techniques do not only allow the translational cooling of the molecules, but also a precise reparation of their internal quantum state. Thus, by an accurate preparation of both the energy and state of the reaction partners as well as by the application of external electric, magnetic or optical fields, prospects open up to study and control chemical processes at an unprecedented level of accuracy. In this chapter, we will review salient theoretical concepts and recent experimental developments for studies of ion-molecule reactions at low temperatures. We first discuss the theoretical background for the description of low-energy ion-molecule reactions. Next we present key experimental methods for laboratory studies of cold ion-molecule reactions. The chapter concludes with a review of illustrative results and an outlook on future directions.
We use quantum and classical adiabatic capture theories to study the chemical reaction Li + CaH LiH + Ca. Using a recently developed ab initio potential energy surface, which provides an accurate representation of long-range interactions in the entrance reaction channel, we calculate the adiabatic channel potentials by diagonalizing the Li-CaH Hamiltonian as a function of the atom-molecule separation. The resulting adiabatic channel potentials are used to calculate both the classical and quantum capture probabilities as a function of collision energy, as well as the temperature dependencies of the partial and total reaction rates. The calculated reaction rate agrees well with the measured value at 1 K (V Singh et al 2012 Phys. Rev. Lett. 108 203201), suggesting that the title reaction proceeds without an activation barrier. The calculated classical adiabatic capture rate agrees well with the quantum result in the multiple-partial-wave regime of relevance to the experiment. Significant differences are found only in the ultracold limit ( mK), demonstrating that adiabatic capture theories can predict the reaction rates with nearly quantitative accuracy in the multiple-partial-wave regime.