An a b i n i t i o study of the reaction of atomic hydrogen with sulfur dioxide

Abstract

The potential energy surface for H(1 2S)+SO2 has been investigated computationally in order to study the catalytic removal of atomic hydrogen in flames by sulfur dioxide. HF/3–21G(*) and MP2/3–21G(*) levels of theory were employed to locate stationary points, which were then characterized by calculation of the vibrational frequencies. Some geometries were also optimized with the 6–31G* basis set. Two adducts HOSO and HSO2, with H bonded to O or S, respectively, were studied. Energies were estimated at the optimized geometries using spin-projected MP4/6–31G* calculations, which show that planar cis HOSO is more stable than Cs HSO2. An H–OSO bond energy of 109 kJ mol−1 is predicted. By contrast HSO2 is predicted to be 25 kJ mol−1 endothermic with respect to H+SO2, and is insufficiently stable to be significant in combustion chemistry. Transition states were located and the information used to derive the kinetics of H+SO2+Ar⇄HOSO+Ar from 298 to 2000 K. An unusually large energy barrier to recombination, of about 95 kJ mol−1 relative to H+SO2, is proposed. The results are compared with available kinetic measurements. Other potential decomposition channels for HOSO, to SO+OH and isomerization to HSO2, were also analyzed.