A quantum-rovibrational-state-selected study of the reaction in the collision energy range of 0.05–10.00 eV: translational, rotational, and vibrational energy effects

Abstract

We report detailed absolute integral cross sections (σ's) for the quantum-rovibrational-state-selected ion–molecule reaction in the center-of-mass collision energy (E_cm) range of 0.05–10.00 eV, where (v⁺₁v⁺₂v⁺₃) = (000), (100), and (020), and . Three product channels, HCO⁺ + OH, HOCO⁺ + H, and CO⁺ + H₂O, are identified. The measured σ(HCO⁺) curve [σ(HCO⁺) versus E_cm plot] supports the hypothesis that the formation of the HCO⁺ + OH channel follows an exothermic pathway with no potential energy barriers. Although the HOCO⁺ + H channel is the most exothermic, the σ(HOCO⁺) is found to be significantly lower than the σ(HCO⁺). The σ(HOCO⁺) curve is bimodal, indicating two distinct mechanisms for the formation of HOCO⁺. The σ(HOCO⁺) is strongly inhibited at E_cm < 0.4 eV, but is enhanced at E_cm > 0.4 eV by (100) vibrational excitation. The E_cm onsets of σ(CO⁺) determined for the (000) and (100) vibrational states are in excellent agreement with the known thermochemical thresholds. This observation, along with the comparison of the σ(CO⁺) curves for the (100) and (000) states, shows that kinetic and vibrational energies are equally effective in promoting the CO⁺ channel. We have also performed high-level ab initio quantum calculations on the potential energy surface, intermediates, and transition state structures for the titled reaction. The calculations reveal potential barriers of ≈0.5–0.6 eV for the formation of HOCO⁺, and thus account for the low σ(HOCO⁺) and its bimodal profile observed. The E_cm enhancement for σ(HOCO⁺) at E_cm ≈ 0.5–5.0 eV can be attributed to the direct collision mechanism, whereas the formation of HOCO⁺ at low E_cm < 0.4 eV may involve a complex mechanism, which is mediated by the formation of a loosely sticking complex between HCO⁺ and OH. The direct collision and complex mechanisms proposed also allow the rationalization of the vibrational inhibition at low E_cm and the vibrational enhancement at high E_cm observed for the σ(HOCO⁺).