Mechanisms and Thermochemistry of Reactions of SiO and Si₂O₂ with OH and H₂O

This paper reports on computational studies of gas-phase reactions of SiO and Si₂O₂. The oxidation of SiO can initiate efficient formation of silica or silicate dust particles in a wide range of environments. Both OH radicals and H₂O molecules are often present in these environments, and their reactions with SiO and the smallest SiO cluster, Si₂O₂, affect the efficiency of eventual dust formation. Density functional theory calculations on these reactions, benchmarked against accurate coupled cluster calculations, indicate that the Si₂O₂ + OH reaction should be faster than SiO + OH. The reaction SiO + H₂O → SiO₂ + H₂ is both endothermic and has high activation energies to reaction. Instead, the formation of molecular complexes is efficient. The reaction of Si₂O₂ with H₂O, which has been suggested as efficient for producing Si₂O₃, might not be as efficient as previously thought. If the H₂O molecules dissociate to form OH radicals, oxidation of SiO and Si₂O₂ could be accelerated instead.