Theoretical studies on the reactions of acetone with chlorine atom and methyl radical

摘要

Theoretical investigations are carried out on the reaction multi-channel CH3COCH3 + Cl (R1) and CH3 COCH3 + CH3 (R2) by means of direct dynamics methods. The minimum energy path (MEP) is obtained at the MP2/6-31 + G(d,p) level, and energetic information is further refined at the BMC–CCSD (single-point) level. The rate constants are calculated by the improved canonical variational transition state theory (ICVT) with the small-curvature tunneling (SCT) correction in a wide temperature range 200–3,000 K. The theoretical overall rate constants are in good agreement with the available experimental data and are found to be k 1 = 3.08 × 10?17 T 2.03exp(?32.96/T) and k 2 = 1.61 × 10?23 T 3.53 exp(?3969.51/T) cm3molecule?1s?1.