Charge Transfer Reactions between Water Isotopologues and Kr(+) ions

[Image: see text] Astrochemical models often adopt capture theories to predict the behavior of experimentally unmeasured ion–molecule reactions. Here, reaction rate coefficients are reported for the charge transfer reactions of H(2)O and D(2)O molecules with cold, trapped Kr(+) ions. Classical capture theory predictions are found to be in excellent agreement with the experimental findings. A crossing point identified between the reactant and product potential energy surfaces, constructed from high-level ab initio calculations, further supports a capture-driven mechanism of charge transfer. However, ion–molecule reactions do not always agree with predictions from capture theory models. The appropriateness of using capture theory-based models in the absence of detailed experimental or theoretical studies is discussed, alongside an analysis of why capture theory is appropriate for describing the likelihood of charge transfer between Kr(+) and the two water isotopologues.