Hydroxyl radical initiated oxidation of formic acid on mineral aerosols surface: a mechanistic, kinetic and spectroscopic study

Environmental context The presence of air-borne mineral dust containing silicates in atmospheric aerosols should be considered in any exploration of volatile organic compound chemistry. This work reports the mechanisms, relative energies and kinetics of free-radical reactions with formic acid adsorbed on silicate surface models. We find that silicate surfaces are more likely to act as a trap for organic radicals than to have a catalytic effect on their reactions. Abstract Heterogeneous reactions of atmospheric volatile organic compounds on aerosol particles may play an important role in atmospheric chemistry. Silicate particles are present in air-borne mineral dust in atmospheric aerosols, and radical reactions can be different in the presence of these mineral particles. In this work, we use quantum-mechanical calculations and computational kinetics to explore the reaction of a hydroxyl free radical with a formic acid molecule previously adsorbed on several models of silicate surfaces. We find that the reaction is slower and takes place according to a mechanism that is different than the one in the gas phase. It is especially interesting to note that the reaction final products, which are the formyl radical attached to the cluster surface, and a water molecule, are much more stable than those formed in the gas phase, the overall reaction being highly exothermic in the presence of the surface model. This suggests that the silicate surface is a good trap for the formed formyl radical. In addition, we have noted that, if a second hydroxyl radical approaches the adsorbed formyl radical, the formation of carbonic acid on the silicate surface is a highly exothermic and exergonic process. The carbonic acid molecule remains strongly attached to the surface, thus blocking CO2 formation in the formic acid oxidation reaction. The spectroscopic properties of the systems involved in the reaction have been calculated, and interesting frequency shifts have been identified in the main vibration modes.