Theoretical Study of the Energy Disposal Mechanism and the State-Resolved Quantum Dynamics of the H + LiH+ → H2 + Li+ Reaction

Despite several studies in the literature, the detailed quantum state-to-state level mechanism of the astrophysically important exoergic barrierless H + LiH+ -> H-2 + Li+ reaction is yet to be understood. In this work, we have investigated the energy disposal mechanism of the reaction in terms of integral reaction cross section, product internal state distributions, differential cross section, and rate constant. Fully converged and Coriolis coupled quantum mechanical calculations based on a time-dependent wave packet method have been performed at the state-to-state level on the ab initio electronic ground state potential energy surface (PES) constructed by Martinazzo et al. (J. Chem. Phys. 2003,119, 11241-11248). The agreement between the present quantum mechanical and previous quasi-classical results is found even at very low relative translational energies of reagents. A non-statistical inverse Boltzmann vibrational distribution for the product is found. This is attributed to the attractive nature of the underlying PES, which facilitates the excess energy release mostly as product vibration (60-80%). The energy disposal in products is found to be unaffected by the rovibrational excitation of the reagent diatom due to the weak coupling between the vibrational modes of the reagent and the product. The mild effect of collision energy on the product energy disposal is ascribed to the effective coupling between the translational modes of the reagent and the product. It is found that the collisions lead to the formation of the product H-2 in its rovibrationally excited levels.

Automated summary

This study investigates the energy disposal mechanism of the exoergic barrierless H + LiH+ -> H-2 + Li+ reaction through quantum mechanical calculations, revealing a non-statistical inverse Boltzmann vibrational distribution for the product. The mild effect of rovibrational excitation of the reagent on product energy disposal is found, with collisions leading to the formation of the product H-2 in its rovibrationally excited levels.