We propose, and quantify from first principles, two novel HO(x)-regenerating unimolecular reactions in isoprene oxidation, which are estimated to yield in pristine tropical forest conditions about 0.7 HO(2) and 0.03 OH radicals per isoprene oxidized; it is further argued that the photolabile coproduct of HO(2) can be a major source of OH, with a yield of the order of 1. The newly proposed chemistry could provide a rationalization for the unexpectedly high OH concentrations often observed in forested environments, such as over the Amazon forest in the recent Gabriel campaign.

, and annual average SCI concentrations less than 7 Â 10 3 molecule cm À3. We find that SCI have only a negligible impact on the global gas phase H 2 SO 4 formation or removal of oxygenates, though some contribution around the equatorial belt, and in select regions, cannot be excluded.

The reaction of Criegee intermediates (CI) with NO and RO(2) radicals is studied for the first time by theoretical methodologies; additionally, the reaction of CI with SO(2) molecules is re-examined. The reaction of CI with NO was found to be slow, with a distinct energy barrier. Their reaction with RO(2) radicals proceeds by the formation of a pre-reactive complex followed by addition of the RO(2) radical on the CI carbon over a submerged barrier, leading to a larger peroxy radical and opening the possibility for oligomer formation in agreement with experiment. The impact of singlet biradicals on the reaction of CI with SO(2) is examined, finding a different reaction mechanism compared to earlier work. For larger CI, the reaction with SO(2) at atmospheric pressures mainly yields thermalized sulfur-bearing secondary ozonides. The fate of the CI in the atmosphere is examined in detail, based on observed concentration of a multitude of coreactants in the atmosphere, and estimated rate coefficients available from literature data. The impact of SCI on tropospheric chemistry is discussed.

The chemistry of the atmosphere encompasses a vast number of reactions acting on a plethora of intermediates. These reactions, occurring sequentially and in parallel, give rise to intertwined and irreducible mechanisms describing the complex chemical transformations of organic and inorganic compounds in the atmosphere. The complexity of this system is that it requires combined experimental, theoretical, and modeling approaches to elucidate the characteristics of the individual reactions, and their mutual interaction. In this review, we describe recent results from quantum chemical and theoretical kinetic studies of relevance to atmospheric chemistry. The review first summarizes the most commonly used theoretical methodologies. It then examines the VOC oxidation initiation channels by OH, O(3), NO(3) and Cl, followed by the reactions of the alkyl, alkoxy, alkylperoxy and Criegee intermediates active in the subsequent oxidation steps. Specific systems such as the oxidation of aromatics and the current state of knowledge on OH-regeneration in VOC oxidation are also discussed, as well as some inorganic reactions.