Theoretical studies on the reactions CH3SCH3 with OH, CF3, and CH3 radicals.

Research paper by Hui H Zhang, Gui-Ling GL Zhang, Jing-Yao JY Liu, Miao M Sun, Bo B Liu, Ze-Sheng ZS Li

Indexed on: 14 Jul '10Published on: 14 Jul '10Published in: Journal of Computational Chemistry


The multiple-channel reactions OH + CH(3)SCH(3) → products, CF(3) + CH(3)SCH(3) → products, and CH(3) + CH(3)SCH(3) → products are investigated by direct dynamics method. The optimized geometries, frequencies, and minimum energy path are all obtained at the MP2/6-31+G(d,p) level, and energetic information is further refined by the MC-QCISD (single-point) method. The rate constants for eight reaction channels are calculated by the improved canonical variational transition state theory with small-curvature tunneling contribution over the temperature range 200-3000 K. The total rate constants are in good agreement with the available experimental data and the three-parameter expressions k(1) = 4.73 × 10(-16)T(1.89) exp(-662.45/T), k(2) = 1.02 × 10(-32)T(6.04) exp(933.36/T), k(3) = 3.98 × 10(-35)T(6.60) exp(660.58/T) (in unit of cm(3) molecule(-1) s(-1)) over the temperature range of 200-3000 K are given. Our calculations indicate that hydrogen abstraction channels are the major channels and the others are minor channels over the whole temperature range.