Theoretical study of the thermochemistry and the kinetics of the SFxCl (x = 0–5) series

A systematic thermodynamic and kinetic study of the entire SFxCl (x = 0–5) series has been carried out. High-level quantum chemical composite methods have been employed to derive enthalpy of formation values from calculated atomization and isodesmic energies. The resulting values for the SCl, SFCl, SF2Cl(C1), SF3Cl(Cs), SF4Cl(Cs) and SF5Cl molecules are 28.0, −36.0, −64.2, −134.3, −158.2 and −237.1 kcal mol−1. A comparison with previous experimental and theoretical values is presented. Statistical adiabatic channel model/classical trajectory, SACM/CT, calculations of selected complex-forming and recombination reactions of F and Cl atoms with radicals of the series have been performed between 200 and 500 K. The reported rate coefficients span over the normal range of about 6 × 10−12 and 5 × 10−11 cm3 molecule−1 s−1 expected for this type of barrierless reactions.

Graphical abstractThe potential energy surface for the reaction of F atoms with SF4Cl plays a decisive role for reaction kinetic calculations.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Potential energy surface features of compounds of the SFxCl (x = 0–5) series. ► Quantum-chemical determination of the enthalpy of formation of SFxCl compounds. ► Kinetic analysis of reactions of F and Cl atoms with radicals of the SFxCl series.