The reaction of SH with O2: A theoretical high level investigation

Abstract

The atmospheric interaction of SH with O₂ was investigated using single and multireference theoretical techniques. Several possibilities for the products were tested, the most important being the formation of HSOO. The rate constant for this reaction was calculated as being 4.5 × 10⁻²² cm³ molecule⁻¹ s⁻¹. It is a very slow reaction and the product is unfavorable thermodynamically by 6.07 kcal mol⁻¹ at 298 K. This reaction is not expected to be a significant one in the atmosphere. Our calculations also show that the species SOOH is not bound, and that the decomposition of HSOO will lead to SO + OH. The rate constant of this unimolecular reaction was predicted to be 1.2 × 10⁻¹⁴ s⁻¹.