Anthracene and phenanthrene tropospheric oxidation promoted by the nitrate radical in the gas-phase. Theoretical modelistic study

Abstract

Polycyclic aromatic hydrocarbons and their oxidized derivatives are ubiquitous environmental pollutants that are toxic to different degrees. The NO3 radical is known to be an important actor in fostering nighttime atmospheric chemistry; hence it could elicit some nocturnal PAH-loss processes. In this study the gas phase pathways open to the initial anthracene and phenanthrene NO3 π−radical adducts in the presence of O2, NO and NO2 are examined by Density Functional Theory to ascertain the mechanistic features of their NO3-initiated oxidative degradation. Unimolecular steps involving the initial adducts (ring closures or fragmentation) present rather high free energy barriers and seem unlikely. Regarding bimolecular reactions, any radical present in the tropospheric environment can give an intrinsically fast radical coupling with the initial adducts, thus producing bifunctional closed shell species. The addition of ground state dioxygen is a relatively fast step that is reversible in some cases, less so in others. It entails subsequent reaction steps, which involve the peroxyl radical intermediate and addition and loss of small species as NO, NO3, NO2 and O2. These steps can either trigger a β−fragmentation with formation of a closed shell dialdehyde or formation of a closed shell nitroxy ketone, bifunctional species that appear to be the most likely products when typical tropospheric concentrations are taken into account.