title: Computational exploration of regioselectivity and atmospheric lifetime in NO3-initiated reactions of CH3OCH3and CH3OCH2CH3.
abstract: The NO3-initiated reactions of CH3OCH3and CH3OCH2CH3have been investigated by the BHandHLYP method in conjunction with the 6-311G(d,p) basis set. Thermodynamic and kinetic data are further refined using the comparatively accurate CCSD(T) method. According to the values of reaction enthalpies (ΔHr,298θ) and reaction Gibbs free energies (ΔGr,298θ) from CH3OCH2CH3with NO3system, we find that H-abstraction pathway from the α-CH2group is more exothermic. It is further confirmed by the calculated CH bond dissociation energy of CH3OCH2CH3molecule. All the rate constants, computed through means of canonical variational transition state with small-curvature tunneling correction, are fitted to the three-parameter expressions k1=1.54×10-23T3.34exp(-1035.53/T) and k2=3.55×10-26T4.31exp(-281.24/T)cm3molecule-1s-1and branching ratios are computed over the temperature range 200-600K. The branching ratios are also discussed. The atmospheric lifetimes of CH3OCH3and CH3OCH2CH3determined by the NO3radical are about 270 and 29days, respectively.
authors.affiliation: Institute of Faculty of Chemistry, National & Local United Engineering Lab for Power Battery Northeast Normal University, 130024 Changchun, People's Republic of China.
authors.forename: Jin-Ting
authors.initials: JT
authors.lastname: Ye
authors.affiliation: Institute of Faculty of Chemistry, National & Local United Engineering Lab for Power Battery Northeast Normal University, 130024 Changchun, People's Republic of China.
authors.forename: Feng-Yang
authors.initials: FY
authors.lastname: Bai
authors.affiliation: Institute of Faculty of Chemistry, National & Local United Engineering Lab for Power Battery Northeast Normal University, 130024 Changchun, People's Republic of China.
authors.forename: Shao-Qing
authors.initials: SQ
authors.lastname: Shi
authors.affiliation: Institute of Faculty of Chemistry, National & Local United Engineering Lab for Power Battery Northeast Normal University, 130024 Changchun, People's Republic of China. Electronic address: panxm460@nenu.edu.cn.
authors.forename: Xiu-Mei
authors.initials: XM
authors.lastname: Pan
mesh_terms: D001272:Atmosphere / Q000737:chemistry*; D004583:Electrons; D004987:Ethers / Q000737:chemistry*; D007700:Kinetics; D008958:Models, Molecular; D008968:Molecular Conformation; D009566:Nitrates / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics; D014732:Vibration
chemical_list: D004987:Ethers; D009566:Nitrates
keywords: Atmospheric lifetime; Branching ratio; Transition state