Role of non-statistical effects in deciding the fate of HO3• in the atmosphere

HO3 center dot has been postulated as a reservoir for OH center dot in various atmospheric reactions. Under collision-free conditions, experiments indicate that the lifetime of this species should be more than one microsecond. Interestingly, the binding energy of HO3 center dot is estimated to be similar to 3 kcal mol(-1) by recent experimental as well as theoretical works. The value of the binding energy suggests that the lifetime of HO3 center dot should be in the picosecond range, and with this lifetime, HO3 center dot cannot act as a reservoir for OH center dot. In the present work, using on-the-fly semiclassical dynamics, we argue that if non-RRKM effects are included, the lifetime of HO3 center dot may be higher than that estimated from the binding energy.