Isotopic and quantum-rovibrational-state effects for the ion–molecule reaction in the collision energy range of 0.03–10.00 eV

Abstract

We report detailed quantum-rovibrational-state-selected integral cross sections for the formation of H₃O⁺via H-transfer (σ_HT) and H₂DO⁺via D-transfer (σ_DT) from the reaction in the center-of-mass collision energy (E_cm) range of 0.03–10.00 eV, where (v⁺₁v⁺₂v⁺₃) = (000), (100), and (020) and . The E_cm inhibition and rotational enhancement observed for these reactions at E_cm < 0.5 eV are generally consistent with those reported previously for H₂O⁺ + H₂(D₂) reactions. However, in contrast to the vibrational inhibition observed for the latter reactions at low E_cm < 0.5 eV, both the σ_HT and σ_DT for the H₂O⁺ + HD reaction are found to be enhanced by (100) vibrational excitation, which is not predicted by the current state-of-the-art theoretical dynamics calculations. Furthermore, the (100) vibrational enhancement for the H₂O⁺ + HD reaction is observed in the full E_cm range of 0.03–10.00 eV. The fact that vibrational enhancement is only observed for the reaction of H₂O⁺ + HD, and not for H₂O⁺ + H₂(D₂) reactions suggests that the asymmetry of HD may play a role in the reaction dynamics. In addition to the strong isotopic effect favoring the σ_HT channel of the H₂O⁺ + HD reaction at low E_cm < 0.5 eV, competition between the σ_HT and σ_DT of the H₂O⁺ + HD reaction is also observed at E_cm = 0.3–10.0 eV. The present state-selected study of the H₂O⁺ + HD reaction, along with the previous studies of the H₂O⁺ + H₂(D₂) reactions, clearly shows that the chemical reactivity of H₂O⁺ toward H₂ (HD, D₂) depends not only on E_cm, but also on the rotational and vibrational states of H₂O⁺(X²B₁). The detailed σ_HT and σ_DT values obtained here with single rovibrational-state selections of the reactant H₂O⁺ are expected to be valuable benchmarks for state-of-the-art theoretical calculations on the chemical dynamics of the title reaction.