| Title: | "Understanding the insight into the mechanisms and dynamics of the Cl-initiated oxidation of (CH(3))(3)CC(O)X and the subsequent reactions in the presence of NO and O(2) (X = F, Cl, and Br)" |
| Author(s): | Bai FY; Lv S; Ma Y; Liu CY; He CF; Pan XM; |
| Address: | "Institute of Functional Material Chemistry, National & Local United Engineering Lab for Power Battery, Faculty of Chemistry, Northeast Normal University, 130024, Changchun, People's Republic of China. Institute of Functional Material Chemistry, National & Local United Engineering Lab for Power Battery, Faculty of Chemistry, Northeast Normal University, 130024, Changchun, People's Republic of China. Electronic address: panxm460@nenu.edu.cn" |
| DOI: | 10.1016/j.chemosphere.2016.12.037 |
| ISSN/ISBN: | 1879-1298 (Electronic) 0045-6535 (Linking) |
| Abstract: | "In this work, the density functional and high-level ab initio theories are adopted to investigate the mechanisms and kinetics of reaction of (CH(3))(3)CC(O)X (X = F, Cl, and Br) with atomic chlorine. Rate coefficients for the reactions of chlorine atom with (CH(3))(3)CC(O)F (k(1)), (CH(3))(3)CC(O)Cl (k(2)), and (CH(3))(3)CC(O)Br (k(3)) are calculated using canonical variational transition state theory coupled with small curvature tunneling method over a wide range of temperatures from 250 to 1000 K. The dynamic calculations are performed by the variational transition state theory with the interpolated single-point energies method at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-311++G(d,p) level of theory. Computed rate constant is in good line with the available experimental value. The rate constants for the title reactions are in this order: k(1) |
| Keywords: | "Atmosphere Chlorine/*chemistry Global Warming Hydrocarbons, Chlorinated/*chemistry Kinetics Nitric Oxide/*chemistry Oxidation-Reduction Oxygen/*chemistry Temperature Atmospheric lifetime Chlorine atom Halogenated organic volatile compounds (HVOCs) Rate co;" |
| Notes: | "MedlineBai, Feng-Yang Lv, Shuang Ma, Yuan Liu, Chun-Yu He, Chun-Fang Pan, Xiu-Mei eng England 2016/12/22 Chemosphere. 2017 Mar; 171:49-56. doi: 10.1016/j.chemosphere.2016.12.037. Epub 2016 Dec 10" |
