title: Theoretical dynamic studies on the reaction of CH3C(O)CH3-nFn with the hydroxyl radical and the chlorine atom.
abstract: The mechanisms of the reactions: CH(3)C(O)CH(2)F+OH/Cl-->products (R1/R2) and CH(3)C(O)CF(3)+OH/Cl-->products (R3/R4) are studied over a wide temperature range (200-2000 K) by means of the dual-level direct dynamics method. The optimized geometries and frequencies of the stationary points are calculated at the MP2/cc-pVDZ and B3LYP/6-311G(d,p) levels. The energy profiles of the reactions are then refined with the interpolated single-point-energy method (ISPE) at the BMC-CCSD level. The canonical variational transition-state theory (CVT) with the small-curvature-tunneling (SCT) correction method is used to calculate the rate constants. Using group-balanced isodesmic reactions as working chemical reactions, the standard enthalpies of formation for CH(3)C(O)CH(2)F, CH(3)C(O)CF(3), CH(3)C(O)CHF, CH(2)C(O)CH(2)F, and CH(2)C(O)CF(3) are evaluated at the CCSD(T)/6-311+G(2d,p)//MP2/cc-pVDZ level of theory. The results indicate that the hydrogen abstraction is dominated by removal from the fluoromethyl position rather than from the methyl position.
authors.affiliation: Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun, Jilin 130023, P. R. China.
authors.forename: Yue-Meng
authors.initials: YM
authors.lastname: Ji
authors.forename: Li
authors.initials: L
authors.lastname: Wang
authors.forename: Ze-sheng
authors.initials: ZS
authors.lastname: Li
authors.forename: Jing-yao
authors.initials: JY
authors.lastname: Liu
authors.forename: Chia-chung
authors.initials: CC
authors.lastname: Sun