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Journal of Physics B Atomic Molecular and Optical Physics

The Rb + –Rb collision rate in the energy range of 10 3 –10 4 K

Xiao-Kang Li, Dian-Cheng Zhang, Shuang-Fei Lv, Jinyun Liu, Feng-Dong Jia, Xiaohe Lin, Rui Li, Yong Wu, Xiang-Yuan Xu, Ping Xue, Xiao-Jing Liu, Zhi-Ping Zhong

Published Apr 20, 2020• 1 citation
Publisher

Abstract

Abstract We study both theoretically and experimentally the energy dependence of the low-energy Rb + –Rb total collision rate k ia in the energy range from 10 3 to 10 4 K. We calculate the integral elastic cross-section and the resonant charge-transfer cross-section by the quantum mechanical molecular orbital close-coupling method, and then obtain k ia for temperatures by averaging the cross-sections over a Maxwell–Boltzmann velocity distribution. The experiments are conducted in an ion–neutral hybrid trap, where the Rb + ions are created by photo-ionization of the cold atoms in a magneto-optic trap (MOT) and accumulated in the linear Paul ion trap. The total ion–atom collision rate k ia is measured by monitoring the fluorescence reduction of the steady-state MOT atoms by sequentially introducing photo-ionization and ion–atom collisions. The ion–atom collision energy E col ≈ T i is modified by changing T i due to T i being more than six orders of magnitude larger than the T a of cold atoms. The temperature of ions T i is obtained by comparing the time-of-flight mass spectrometry of Rb + from experimental results to that obtained by SIMION simulation. The equilibrium steady T i is modified by changing the initial root-mean-squared position of the ion cloud, and the k ia are measured with E col from 8000 to 16 000 K. Both the theoretical and experimental results show that k ia increases with E col . More specifically, the measured k ia increases rapidly with the enlargement of E col near 10 000 K. The theoretical calculation results show that k ia increases slowly with E col . The specific difference may be due to the influence of the ratio of excited states f e on the trend of k ia at different E col .

DOI
10.1088/1361-6455/ab8b45

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Abstract We study both theoretically and experimentally the energy dependence of the low-energy Rb + –Rb total collision rate k ia in the energy range from 10 3 to 10 4 K. We calculate the integral elastic cross-section and the resonant charge-transfer cross-section by the quantum mechanical molecular orbital close-coupling method, and then obtain k ia for temperatures by averaging the cross-sections over a Maxwell–Boltzmann velocity distribution. The experiments are conducted in an ion–neutral hybrid trap, where the Rb + ions are created by photo-ionization of the cold atoms in a magneto-optic trap (MOT) and accumulated in the linear Paul ion trap. The total ion–atom collision rate k ia is measured by monitoring the fluorescence reduction of the steady-state MOT atoms by sequentially introducing photo-ionization and ion–atom collisions. The ion–atom collision energy E col ≈ T i is modified by changing T i due to T i being more than six orders of magnitude larger than the T a of cold atoms. The temperature of ions T i is obtained by comparing the time-of-flight mass spectrometry of Rb + from experimental results to that obtained by SIMION simulation. The equilibrium steady T i is modified by changing the initial root-mean-squared position of the ion cloud, and the k ia are measured with E col from 8000 to 16 000 K. Both the theoretical and experimental results show that k ia increases with E col . More specifically, the measured k ia increases rapidly with the enlargement of E col near 10 000 K. The theoretical calculation results show that k ia increases slowly with E col . The specific difference may be due to the influence of the ratio of excited states f e on the trend of k ia at different E col .
An ion–neutral hybrid trap is built to study low-energy ion–atom collisions. The ion–neutral hybrid trap is combined with two spatially concentric traps: a linear Paul trap for the ionic species and a magneto-optical trap (MOT) for the neutral species. The total ion–atom collision rate coefficient between 87 Rb atoms and optically dark 87 Rb + ions is measured by monitoring the reduction of the steady-state MOT atoms by sequentially introducing various mechanisms, namely photoionization and ion–atom collisions. In contrast to other experiments, a concise experimental procedure is devised to obtain the loss rates of the MOT atoms due to photoionization and ion–atom collisions in one experimental cycle, and then the collision rate of cold 87 Rb atoms with 87 Rb + ions is deduced to m 3 / s with K measured by the time of flight of the ion signal. The measurements show good agreement with the collision rate derived from the Langevin model.
This thesis explores the fundamental physical and chemical processes between molecular ions and neutral atoms in the gas phase at very low energies. At temperatures in the mK regime, these are dominated by long-range interactions and only a few partial waves. This study contributes to the understanding of the details of intermolecular interactions and provides valuable data for benchmarking theoretical models and quantum-chemical calculations. Although there is a wide range of previous atomic collision system studies, the investigations of cold collisions with molecular ions are limited. The experimental setup used in this work enabled the measurement of rate coefficients for molecular ion-neutral collisions. The development of a dynamic ion-neutral hybrid trap with improved control over collision energy led to new insights into charge-transfer rate coefficients for molecular ion-neutral atom collisions involving N2+^+_22+​+Rb, O2+^+_22+​+Rb and N2_22​H+^+++Rb. Two different experimental settings enable state-and collision-energy dependent measurements of rate coefficients for all systems revealing an intriguing interplay between long-and short-range effects for the homonuclear diatomics by comparison to theoretical calculations and surprising experimental results for the polyatomic study. A fit of a constant function to the measured CT rate coefficients in the state-dependent experiment of N2_22​H+^+++Rb yielded the similar result as for N2+^+_22+​+Rb(5s5s5s)(2S1/2^2S_{1/2}2S1/2​). In the collision-energy dependent experiment the CT rate coefficient for N2_22​H+^+++Rb(5s5s5s)(2S1/2^2S_{1/2}2S1/2​) and N2_22​H+^+++Rb(5p5p5p)(2P3/2^2P_{3/2}2P3/2​) are both similar to the results for N2+^+_22+​+Rb(5s5s5s)(2S1/2^2S_{1/2}2S1/2​), and also the rate coefficients increase as the collision-energy increases.
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.
We present measurements of the total elastic and resonant charge-exchange ion-atom collision rate coefficient kia{k}_{\mathrm{ia}}kia​ of cold sodium (Na) with optically dark low-energy Na+{\mathrm{Na}}^{+}Na+ ions in a hybrid ion-neutral trap. To determine kia{k}_{\mathrm{ia}}kia​, we measured the trap loading and loss rates from both a Na magneto-optical trap (MOT) and a linear radio-frequency quadrupole Paul trap. We found the total rate coefficient to be $7.4\ifmmode\pm\else\textpm\fi{}1.9\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}8}\phantom{\rule{0.28em}{0ex}}{\mathrm{cm}}^{3}/\mathrm{s}$ for the type-I Na MOT immersed within an $\ensuremath{\approx}140\ensuremath{-}\mathrm{K}$ ion cloud and $1.10\ifmmode\pm\else\textpm\fi{}0.25\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}7}\phantom{\rule{0.28em}{0ex}}{\mathrm{cm}}^{3}/\mathrm{s}$ for the type-II Na MOT within an $\ensuremath{\approx}1070\ensuremath{-}\mathrm{K}$ ion cloud. Our measurements show excellent agreement with previously reported theoretical fully quantal ab initio calculations. In the process of determining the total rate coefficient, we demonstrate that a MOT can be used to probe an optically dark ion cloud's spatial distribution within a hybrid trap.
Cold ion-neutral reactive processes were studied in an hybrid trap down to average collision energies <E_coll>/k_B > 20 mK. The atomic ion-neutral systems Ca^+ + Rb and Ba^+ + Rb were studied, and the results interpreted with high-level quantum chemical and quantum scattering calculations. Three reactive processes were found to be in competition, namely non-radiative charge transfer induced by non-adiabatic couplings between potential energy surfaces, radiative charge transfer, and radiative association of molecular ions, which were observed using mass spectrometry. The role of light in these processes was investigated. Enhancement of reaction rate constants from electronically excited entrance channels was observed and rationalised using computed potential energy curves. The collision-energy dependence of the reaction rate constants was investigated, and was found to be in line with predictions of both classical and quantum models uncovering general effects in cold ion-neutral systems. Cold reactions in the molecular ion-neutral system N_2^+ + Rb were also investigated with average collision energies two orders of magnitude lower than previously realised. The reaction rate constant in this system was found to depend strongly on the Rb ^2P_3/2 population, with the rate constant from the corresponding excited entrance channel being significantly faster than the collision rate predicted by Langevin theory. A classical capture model was developed taking into account the charge permanent-quadrupole intermolecular force and was found to reproduce the observed rate. The implied near unit reaction probability was rationalised by a near electronic resonance of entrance and product channels. A detailed description of the implementation of the ion-neutral hybrid trap is given. A thorough comparison of the results from state-of-the-art experiments and theory reveals general features of light assisted cold ion-neutral reactions. \n