A gas-phase mechanistic investigation of the unimolecular, water/ammonia-assisted decomposition reactions of the a-hydroxy hydroperoxides (HPs) and hydroperoxide arylamines (a-HPs) produced during the styrene ozonolysis has been carried out theoretically in the present article. The instrumental role of stereochemistry in controlling the outcome of individual reactions has been discussed. Thermodynamic parameters (Delta G(298K), Delta H-298(K), Delta E-0K) associated with individual reactions have also been computed. The rate constants estimated for individual reactions using conventional transition state theory (TST) combined with statistical mechanics provide a comprehensive understanding of the reaction mechanism and also elucidate the atmospheric fate of Criegee intermediates. Considering the feasibility of reactions from thermodynamic and kinetic points of view, while aldehyde (PhCHO) formation pathway originating from bimolecular decomposition of HP is found to be kinetically favored, benzoic acid formation pathway remains favored thermodynamically. A similar consideration for the bimolecular reactions of a-HP reveals the phenylmethanimine formation pathway to be kinetically favored, while the benzamide formation pathway is favored thermodynamically. Our findings appear to be in excellent agreement with the experimental observations.