Abstract
The channel specific and initial state-selected reaction cross section and temperature-dependent rate constant for the title system is calculated with the aid of a time-dependent wave-packet approach and using the ab initio potential energy surface of Dunne et al. [Chem. Phys. Lett. 336, 1 (2001)]. All partial-wave contributions up to the total angular momentum J=74 are explicitly calculated within the coupled states (CS) approximation. Companion calculations are also carried out employing the standard as well as the uniform J-shifting (JS) approximation. The overall variation of reaction cross sections corresponds well to the behavior of a barrierless reaction. The hydrogen exchange channel yielding HLi+H products is seen to be more favored over the HLi depletion channel yielding Li+H(2) products at low and moderate collision energies. Sharp resonance features are observed in the cross-section results for the HLi depletion channel at low energies. Resonance features in the reaction cross sections average out with various partial-wave contributions, when compared to the same observed in the individual reaction probability curve. Except near the onset of the reaction, the vibrational and rotational excitation of the reagent HLi, in general, does not dramatically influence the reactivity of either channel. The thermal rate constants calculated up to 4000 K show nearly Arrhenius type behavior. The rate constant decreases with vibrational excitation of the reagent HLi, indicating that the cold HLi molecules are efficiently depleted in the reactive encounter with H at relatively low temperatures. The results obtained from the JS approximation are found to agree well qualitatively with the CS results.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.