Kinetics and thermochemistry of chlorine- and nitrogen-containing oxides and peroxides

A valence bond additivity scheme based on established thermochemical data is able to reproduce the heats of formation of novel species such as O_2ClONO_2, ClOClO_2, ONONO_2, ClOONO, HOONO, FOClO_3, and FONO within ±2 kcal/mol. This finding, together with recently obtained values of ΔH_f^o(ClO_3(g)) and ΔH_^fo(ClO_4(g)), makes possible a general analysis of the thermal stabilities of known or conceivable chlorine and nitrogen oxides of potential atmospheric significance. Radical mechanisms for the decompositions of chlorine hexoxide and perchloric acid are also discussed.