Efficient quantum-classical method for computing thermal rate constant of recombination: Application to ozone formation

Efficient method is proposed for computing thermal rate constant of recombination reaction that proceeds according to the energy transfer mechanism, when an energized molecule is formed from reactants first, and is stabilized later by collision with quencher. The mixed quantum-classical theory for the collisional energy transfer and the ro-vibrational energy flow [M. Ivanov and D. Babikov, J. Chem. Phys. 134, 144107 (2011)] is employed to treat the dynamics of molecule + quencher collision. Efficiency is achieved by sampling simultaneously (i) the thermal collision energy, (ii) the impact parameter, and (iii) the incident direction of quencher, as well as (iv) the rotational state of energized molecule. This approach is applied to calculate third-order rate constant of the recombination reaction that forms the (OOO)-O-16-O-18-O-16 isotopomer of ozone. Comparison of the predicted rate vs. experimental result is presented. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4711760]