Journal of computational chemistry

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

PMID 20623699


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.

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