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We have measured the merged-beams rate coefficient for the titular isotope exchange reactions as a function of the relative collision energy in the range of ∼ 3 meV–10 eV. The results appear to scale with the number of available sites for deuteration. We have performed extensive theoretical calculations to characterize the zero-point energy corrected reaction path. Vibrationally adiabatic minimum energy paths were obtained using a combination of unrestricted quadratic configuration interaction of single and double excitations and internally contracted multireference configuration interaction calculations. The resulting barrier height, ranging from 68 meV to 89 meV, together with the various asymptotes that may be reached in the collision, was used in a classical over-the-barrier model. All competing endoergic reaction channels were taken into account using a flux reduction factor. This model reproduces all three experimental sets quite satisfactorily. In order to generate thermal rate coefficients down to 10 K, the internal excitation energy distribution of each H 3 + isotopologue is evaluated level by level using available line lists and accurate spectroscopic parameters. Tunneling is accounted for by a direct inclusion of the exact quantum tunneling probability in the evaluation of the cross section. We derive a thermal rate coefficient of < 1 × 1 0 − 12 c m 3 s − 1 for temperatures below 44 K, 86 K, and 139 K for the reaction of D with H 3 + , H 2 D + , and D 2 H + , respectively, with tunneling effects included. The derived thermal rate coefficients exceed the ring polymer molecular dynamics prediction of Bulut et al. [J. Phys. Chem. A 123, 8766 (2019)] at all temperatures. [ABSTRACT FROM AUTHOR]

Although different ion-atom collisions have been studied in various contexts, precise values of cross-sections for many atomic processes were seldom obtained. One of the main uncertainties originates from the value of target densities. In this paper, we describe a unique method to measure a target density precisely with a combination of physical vapor deposition and inductively coupled plasma optical emission spectrometry. This method is preliminarily applied to a charge transfer cross-section measurement in collisions between highly charged ions and magnesium vapor. The final relative uncertainty of the target density is less than 2.5%. This enables the precise studies of atomic processes in ion-atom collisions, even though in the trial test the deduction of precise capture cross-sections was limited by other systematic errors. [ABSTRACT FROM AUTHOR]