Theoretical study of the molecular properties and the formation kinetics of the FS(O 2)OCO radical

• Published in: Chemical physics letters Vol. 490; no. 4; pp. 127 - 131
• Main Authors: Tucceri, M.E., Bracco, L.B., Cobos, C.J.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 26.04.2010
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/j.cplett.2010.03.036

Conformational mobilities, vibrational frequencies and the enthalpy of formation of FS(O 2)OCO have been calculated by using DFT and ab initio methods. The reaction FSO 3 + CO → FS(O 2)OCO was analyzed by transition state theory. Molecular and kinetics properties of the FS(O 2)OCO radical have been studied. Equilibrium structure, harmonic vibrational frequencies, conformational mobilities, enthalpy of formation of this radical and the energetic of the reaction FSO 3 + CO → FS(O 2)OCO have been investigated at different levels of the density functional theory and of the Gaussian composite models. The standard enthalpy of formation for FS(O 2)OCO is predicted to be Δ H f ,298 = −155.0 kcal mol −1. In very good agreement with reported experimental values, a rate coefficient at 296 K of 3.6 × 10 −17 cm 3 molecule −1 s −1 and an activation energy of 7.6 kcal mol −1 have been calculated.