Theoretical kinetic study of the reaction of SF5 radical with F2, Cl2 and SF5

CRISTIAN BUENDÍA-ATENCIO; CARLOS J. COBOS.; ADELA E. CROCE; GILLES P. PIEFFET

Computational and Theoretical Chemistry

Elsevier

Lugar: Amsterdam; Año: 2016 vol. 1090 p. 41 - 46

2210-271X

A kinetic study of the gas phase reaction of the SF5 radical with the species F2, Cl2 andSF5 has been performed. Quantum chemical calculations employing the DFT methodsB3LYP, BMK, MPWB1K, BB1K and M06-2X combined with the 6-311+G(3df) basisset provide the required relevant parts of the potential energy surfaces. Transition statetheory calculations for the SF5 + F2 → SF6 + F reaction lead to the rate coefficient 1.4 x10-12 exp(-4.1 kcal mol-1/RT) cm3 molecule-1 s-1 at 213 ? 245 K. From similarcalculations, the expression 2.1 x 10-11 exp(-7.6 kcal mol-1/RT) cm3 molecule-1 s-1 wasobtained for SF5 + Cl2 → SF5Cl + Cl. The combination of the rate coefficients obtainedfor the F atom abstraction reaction with reported experimental kinetic information yieldsthe value 3 x 10-12 cm3 molecule-1 s-1 for the SF5 + SF5 → S2F10 association reaction. A comparison with SACM/CT calculations and previous conflicting rate coefficients forthis process is presented.