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arXiv:2006.05906 · Journal of Physics Conference Series

Cold collisions of C2− with Li and Rb atoms in hybrid traps

Milaim Kas, Jacques Liévin, Nathalie Vaeck, Jérôme Loreau

Published Jan 1, 2020• 3 citations
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Abstract

Abstract We present a theoretical investigation of reactive and non-reactive collisions of Li and Rb atoms with C 2 − molecular anions at low temperatures in the context of sympathetic cooling in hybrid trap experiments. Based on accurate potential energy surfaces for the singlet and triplet states of the Li– C 2 − and Rb– C 2 − systems, we show that the associative electronic detachment reaction is inefficient but that it occurs with a large rate for collisions involving excited states of either Li/Rb or C 2 − . We also investigate rotationally inelastic collisions in order to explore the cooling of the translational and rotational degrees of freedom of C 2 − in hybrid ion-atom traps. The effect of micromotion is taken into account by considering Tsallis distributions of collision energies. We show that the translational cooling occurs much more rapidly than rotational cooling and that the presence of excited atoms leads to losses of anions on a timescale comparable to that of rotational cooling.

DOI
10.1088/1742-6596/1412/6/062003

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Abstract We present a theoretical investigation of reactive and non-reactive collisions of Li and Rb atoms with C 2 − molecular anions at low temperatures in the context of sympathetic cooling in hybrid trap experiments. Based on accurate potential energy surfaces for the singlet and triplet states of the Li– C 2 − and Rb– C 2 − systems, we show that the associative electronic detachment reaction is inefficient but that it occurs with a large rate for collisions involving excited states of either Li/Rb or C 2 − . We also investigate rotationally inelastic collisions in order to explore the cooling of the translational and rotational degrees of freedom of C 2 − in hybrid ion-atom traps. The effect of micromotion is taken into account by considering Tsallis distributions of collision energies. We show that the translational cooling occurs much more rapidly than rotational cooling and that the presence of excited atoms leads to losses of anions on a timescale comparable to that of rotational cooling.
We present a theoretical investigation of cold reactive and nonreactive collisions of Li and Rb atoms with ${\mathrm{C}}_{2}{}^{\ensuremath{-}}$. The potential energy surfaces for the singlet and triplet states of the $\mathrm{Li}\ensuremath{-}{\mathrm{C}}_{2}{}^{\ensuremath{-}}$ and $\mathrm{Rb}\ensuremath{-}{\mathrm{C}}_{2}{}^{\ensuremath{-}}$ systems have been obtained using the CASSCF followed by ic-MRCI approach with extended basis sets. The potential energy surfaces are then used to investigate the associative detachment reaction and to calculate rotationally inelastic cross sections at low collision energies by means of the close-coupling method. The results are compared to those obtained for other anionic systems such as $\mathrm{Rb}\ensuremath{-}{\mathrm{OH}}^{\ensuremath{-}}$, and the implications for hybrid-trap experiments and sympathetic cooling experiments are explored. Furthermore, we discuss the possibility to perform Doppler thermometry on the ${\mathrm{C}}_{2}{}^{\ensuremath{-}}$ anion and investigate the collision process involving excited electronic states.
This dissertation reports sympathetic cooling of the molecular hydroxyl anion (OH– ) via collisions with ultra cold rubidium (Rb) atoms. The anion’s translational and rotational degrees of freedom were cooled simultaneously. A new generation hybrid atom-ion trap (HAITrap) has been set up, combining an octupole radio frequency (rf) trap for ion storage and a dark-spontaneous force optical trap (darkSPOT) for Rb atoms. While the octupole rf-trap provides a large rf-field-free region decreasing rf-induced collisional heating, the darkSPOT reinforces this effect by locating the atom cloud in the center of the ion trap. The darkSPOT also enables to generate large dark state fractions, suppressing associative detachment and thus ion losses. Evidence on translational sympathetic cooling in the HAITrap was provided using two methods of kinetic thermometry: photodetachment tomography (PD) and measurements of the time of flight (ToF) distribution. The ToF analysis has shown to be more conclusive and numerical simulations validated the experimental findings qualitatively. Based on a one dimensional ToF-temperature mapping, the narrowest measured energy spread would correspond to a temperature of 35 ± 5K. Deviations from thermal distributions were observed, as predicted from a theoretical model developed by our group. Rotational sympathetic cooling was observed via state selective photodetachment (SSPD). This was performed by pre-cooling the atoms with helium buffer gas at 295K and further cooling the ions with Rb at 300 μK. SSPD thermometry yielded a 70% decrease of the anions rotational temperature after interaction with Rb. These experimental findings could have direct applications in cold collision studies, quantum control of chemical reactions or sympathetic cooling of anti-protons.
We report on a study of cold reactive collisions between sympathetically cooled molecular ions and laser-cooled atoms in an ion-atom hybrid trap. Chemical reactions were studied at average collision energies <E(coll)>/k(B)>/~20 mK, about 2 orders of magnitude lower than has been achieved in previous experiments with molecular ions. Choosing N(2)(+)+Rb as a prototypical system, we find that the reaction rate is independent of the collision energy within the range studied, but strongly dependent on the internal state of Rb. Highly efficient charge exchange four times faster than the Langevin rate was observed with Rb in the excited (5p) (2)P(3/2) state. This observation is rationalized by a capture process dominated by the charge-quadrupole interaction and a near resonance between the entrance and exit channels of the system. Our results provide a test of classical models for reactions of molecular ions at the lowest energies reached thus far.
We report close-coupling (CC) quantum dynamics calculations for collisional excitation/de-excitation of the lowest four rotational levels of OD − and of OH − interacting with Rb atoms in a cold ion trap. The calculations are carried out over a range of energies capable of yielding the corresponding rates for state-changing events over a rather broad interval of temperatures which cover those reached in earlier cold trap experiments. They involved sympathetic cooling of the molecular anion through a cloud of laser-cooled Rb atoms, an experiment which is currently being run again through a Heidelberg–Innsbruck collaboration. The significance of isotopic effects is analysed by comparing both systems and the range of temperatures examined in the calculations is extended up to 400 K, starting from a few mK. Both cross sections and rates are found to be markedly larger than in the case of OD − /OH − interacting the He atoms under the same conditions, and the isotopic effects are also seen to be rather significant at the energies examined in the present study. Such findings are discussed in the light of the observed trap losses of molecular anions.
Cold chemical reactions between laser-cooled Ca+ ions and Rb atoms were studied in an ion-atom hybrid trap. Reaction rate constants were determined in the range of collision energies ⟨E coll⟩/k B=20 mK-20 K. The lowest energies were achieved in experiments using single localised Ca+ ions. Product branching ratios were studied using resonant-excitation mass spectrometry. The dynamics of the reactive processes in this system (non-radiative and radiative charge transfer as well as radiative association leading to the formation of CaRb+ molecular ions) have been analysed using high-level quantum-chemical calculations of the potential energy curves of CaRb+ and quantum-scattering calculations for the radiative channels. For the present low-energy scattering experiments, it is shown that the energy dependence of the reaction rate constants is governed by long-range interactions in line with the classical Langevin model, but their magnitude is determined by short-range non-adiabatic and radiative couplings which only weakly depend on the asymptotic energy. The quantum character of the collisions is predicted to manifest itself in the occurrence of narrow shape resonances at well-defined collision energies. The present results highlight both universal and system-specific phenomena in cold ion-neutral reactive collisions.
Cold chemical reactions between laser-cooled Ca^+ ions and Rb atoms were studied in an ion-atom hybrid trap. Reaction rate constants were determined in the range of collision energies /k_B = 20 mK-20 K. The lowest energies were achieved in experiments using single localized Ca^+ ions. Product branching ratios were studied using resonant-excitation mass spectrometry. The dynamics of the reactive processes in this system (non-radiative and radiative charge transfer as well as radiative association leading to the formation of CaRb^+ molecular ions) have been analyzed using high-level quantum-chemical calculations of the potential energy curves of CaRb^+ and quantum-scattering calculations for the radiative channels. For the present low-energy scattering experiments, it is shown that the energy dependence of the reaction rate constants is governed by long-range interactions in line with the classical Langevin model, but their magnitude is determined by short-range non-adiabatic and radiative couplings which only weakly depend on the asymptotic energy. The quantum character of the collisions is predicted to manifest itself in the occurrence of narrow shape resonances at well-defined collision energies. The present results highlight both universal and system-specific phenomena in cold ion-neutral reactive collisions.