Resonances of CH2(a 1A1) and their roles in unimolecular and bimolecular reactions

Low-lying resonances of the CH2(a 1A1) system (J=0) in an accurate ab initio potential energy surface are studied using a filter-diagonalization method. The width of these resonances fluctuates by more than two orders of magnitude and on average increases with the energy. Analysis of the resonance states concludes that the unimolecular decay of the excited molecular system near the dissociation threshold is neither mode specific nor statistical state specific. This is apparently due to remnant regularity embedded in the largely chaotic classical phase space, as evidenced by periodic orbit analysis. As a result, the Rice-Ramsperger-Kassel-Marcus and statistical adiabatic channel models overestimate the average unimolecular decay rate. The implications of the resonances for the bimolecular C(1D)+H2 reaction are also discussed.