COLLISIONAL RECOMBINATION REACTION H-2+M-]HO2+M - QUANTUM-MECHANICAL STUDY USING FILTER DIAGONALIZATION(O)

We report the results of calculations for the collisional recombinatio n rate of the reaction H+O-2+M-->HO2+M. This study uses the recently d eveloped quantum mechanical theory of recombination (within the strong collision approximation) based on the flux-flux correlation function analysis [J. Phys. Chem. 99, 12387 (1995)]. The quantum dynamics calcu lations are based on the new very efficient computational procedure of filter diagonalization [J. Chem. Phys. 103, 10074 (1995)]. This proce dure allows one to obtain individual complex eigenenergies and eigenfu nctions of a large non-Hermitian matrix representation of the Hamilton ian with an absorbing potential. The computed rates are compared to th e Lindemann steady-state approximation result. The latter leads to an overestimation of the rate since it does not take into account the res onance interference effects. This becomes more critical at higher temp eratures where many bread high energy overlapping resonances contribut e to the rate. (C) 1996 American Institute of Physics.