STATE-TO-STATE QUANTUM WAVE PACKET DYNAMICS OF THE LiH + H REACTION ON TWO AB INITIO POTENTIAL ENERGY SURFACES

Abstract

The dynamics and kinetics of the LiH + H reaction have been studied by using an accurate quantum reactive time-dependent wave packet method on the ab initio ground electronic state potential energy surfaces (PES) developed earlier. Reaction probabilities for the two possible reaction channels, the LiH?+?H? H2?+?Li depletion process and the LiH + H?H + LiH hydrogen exchange reaction, have been calculated from 1?meV up to 1.0?eV collision energies for total angular momenta J from 0 to 80. State-to-state and total integral cross sections for the LiH-depletion and H-exchange channels of the reaction have been calculated over this collision energy range. It is found that the LiH-depletion channel is dominant in the whole range of collision energies for both PESs. Accurate total rate coefficients have been calculated on both surfaces from 100?K to 2000?K and are significantly larger than previous empirical estimates and previous J-shifting results. In addition, the present accurate calculations present noticeable differences with previous calculations using the centrifugal sudden approximation.