Quantum wave-packet dynamics of H+HLi scattering: Reaction cross section and thermal rate constant

摘要: The channel specific and initial state-selected reaction cross section temperature-dependent rate constant for the title system is calculated with aid of a time-dependent wave-packet approach using ab initio potential energy surface Dunne et al. [Chem. Phys. Lett. 336, 1 (2001)]. All partial-wave contributions up to total angular momentum J=74 are explicitly within coupled states (CS) approximation. Companion calculations also carried out employing standard as well uniform J-shifting (JS) overall variation sections corresponds behavior barrierless reaction. hydrogen exchange yielding HLi+H products seen be more favored over HLi depletion Li+H(2) at low moderate collision energies. Sharp resonance features observed in cross-section results Resonance average various contributions, when compared same individual probability curve. Except near onset reaction, vibrational rotational excitation reagent HLi, general, does not dramatically influence reactivity either channel. thermal constants 4000 K show nearly Arrhenius type behavior. decreases indicating that cold molecules efficiently depleted reactive encounter H relatively temperatures. obtained from JS approximation found agree qualitatively CS results.