title: Mechanistic and kinetic study on the reaction of ozone and trans-2-chlorovinyldichloroarsine.
abstract: Singlet and triplet potential energy surfaces for the atmospheric ozonation of trans-2-chlorovnyldichloroarsine (lewisite) are investigated theoretically. Optimizations of the reactants, products, intermediates and transition states are carried out at the BHandHLYP/6-311+G(d,p) level. Single point energy calculations are performed at the CCSD(T)/6-311+G(d,p) level based on the optimized structures. The detailed mechanism is presented and discussed. Various possible H (or Cl)-abstraction and C (or As)-addition/elimination pathways are considered. The results show that the As-addition/elimination is more energetically favorable than the other mechanisms. Rice-Ramsperger-Kassel-Marcus (RRKM) theory is used to compute the rate constants over the possible atmospheric temperature range of 200-3000 K and the pressure range of 10(-8)-10(9) Torr. The calculated rate constant is in good agreement with the available experimental data. The total rate coefficient shows positive temperature dependence and pressure independence. The modified three-parameter Arrhenius expressions for the total rate coefficient and individual rate coefficients are represented. Calculation results show that major product is CHClCHAs(OOO)Cl2 (s-IM3) at the temperature below 600 K and O2 + CHClCHAsOCl2 (s-P9) play an important role at the temperature between 600 and 3000 K. Time-dependent DFT (TD-DFT) calculations indicate that CHCl(OOO)CHAsCl2 (s-IM3) and CHOAsCl2 (s-P5) can take photolysis easily in the sunlight. Due to the absence of spectral information for arsenide, computational vibrational spectra of the important intermediates and products are also analyzed to provide valuable evidence for subsequent experimental identification.
authors.affiliation: Institute of Functional Material Chemistry, Faculty of Chemistry, National & Local United Engineering Lab for Power Battery, Northeast Normal University, Renmin Road 5268, Changchun, Jilin, 130024, PR China.
authors.forename: Wanqiao
authors.initials: W
authors.lastname: Zhang
authors.affiliation: Institute of Functional Material Chemistry, Faculty of Chemistry, National & Local United Engineering Lab for Power Battery, Northeast Normal University, Renmin Road 5268, Changchun, Jilin, 130024, PR China. Electronic address: sunh600@nenu.edu.cn.
authors.forename: Hao
authors.initials: H
authors.lastname: Sun
authors.affiliation: Institute of Functional Material Chemistry, Faculty of Chemistry, National & Local United Engineering Lab for Power Battery, Northeast Normal University, Renmin Road 5268, Changchun, Jilin, 130024, PR China.
authors.forename: Wei
authors.initials: W
authors.lastname: Chen
authors.affiliation: Key Laboratory of Photoinduced Functional Materials, Mianyang Normal University, Mianyang, 621000, PR China.
authors.forename: Yunju
authors.initials: Y
authors.lastname: Zhang
authors.affiliation: Institute of Functional Material Chemistry, Faculty of Chemistry, National & Local United Engineering Lab for Power Battery, Northeast Normal University, Renmin Road 5268, Changchun, Jilin, 130024, PR China.
authors.forename: Fengdi
authors.initials: F
authors.lastname: Wang
authors.affiliation: Institute of Functional Material Chemistry, Faculty of Chemistry, National & Local United Engineering Lab for Power Battery, Northeast Normal University, Renmin Road 5268, Changchun, Jilin, 130024, PR China.
authors.forename: Shuwei
authors.initials: S
authors.lastname: Tang
authors.affiliation: Institute of Functional Material Chemistry, Faculty of Chemistry, National & Local United Engineering Lab for Power Battery, Northeast Normal University, Renmin Road 5268, Changchun, Jilin, 130024, PR China.
authors.forename: Jingping
authors.initials: J
authors.lastname: Zhang
authors.affiliation: Chemical Defense Research Institute of Beijing, Beijing, 102205, PR China. Electronic address: wangrs@nenu.edu.cn.
authors.forename: Haitao
authors.initials: H
authors.lastname: Wang
authors.affiliation: Institute of Functional Material Chemistry, Faculty of Chemistry, National & Local United Engineering Lab for Power Battery, Northeast Normal University, Renmin Road 5268, Changchun, Jilin, 130024, PR China. Electronic address: dr.wanghaitao@gmail.com.
authors.forename: Rongshun
authors.initials: R
authors.lastname: Wang
mesh_terms: D000393:Air Pollutants / Q000032:analysis* / Q000737:chemistry / Q000528:radiation effects; D001152:Arsenicals / Q000032:analysis* / Q000737:chemistry / Q000528:radiation effects; D002619:Chemical Warfare Agents / Q000032:analysis* / Q000737:chemistry / Q000528:radiation effects; D007700:Kinetics; D008962:Models, Theoretical; D010126:Ozone / Q000737:chemistry*; D010782:Photolysis; D011312:Pressure; D013696:Temperature
chemical_list: D000393:Air Pollutants; D001152:Arsenicals; D002619:Chemical Warfare Agents; C035965:lewisite; D010126:Ozone
keywords: IR spectra; Ozone; RRKM; Reaction mechanism; UV–Vis spectra