title: The mechanistic study of the hydroxyl radical reaction with trans-2-chlorovinyldichloroarsine.
abstract: The trans-2-chlorovinyldichloroarsine (Lewisite) was produced and handled during WWI and WWII as chemical warfare agents. It was very difficult to explore its chemical characterization by experiments ways. The quantum chemical calculations proved to be a precise and harmless method for the toxicological system. In this paper, the gas phase reaction mechanisms of OH radical with trans-2-chlorovinyldichloroarsine (lewisite) were studied by second-order Møller-Plesset perturbation theory (MP2) method. The geometries of reactants, products, complexes, and transition states were optimized at the MP2/6-311++G(d,p) level. To gain more accurate mechanistic knowledge, the single-point energies were calculated using G3 and CCSD(T) method. This reaction exhibited three mechanisms, namely, direct hydrogen abstraction, direct chlorine abstraction, and addition/elimination. Multichannel Rice-Ramsperger-Kassel-Marcus theory and transition-state theory have been carried out for overall and individual rate constants over a wide range of temperatures and pressures. The computational results indicated that addition/elimination reaction is more favorable than direct hydrogen abstraction and direct chlorine abstraction. The major products for the total reaction are AsCl2 and CHClCH2O generated via C(2)-addition/elimination.
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, People's Republic of China, zhangwj594@nenu.edu.cn.
authors.forename: Wanqiao
authors.initials: W
authors.lastname: Zhang
authors.forename: Xiaodi
authors.initials: X
authors.lastname: Guo
authors.forename: Yunju
authors.initials: Y
authors.lastname: Zhang
authors.forename: Fang
authors.initials: F
authors.lastname: Wang
authors.forename: Haijie
authors.initials: H
authors.lastname: Shi
authors.forename: Jingping
authors.initials: J
authors.lastname: Zhang
authors.forename: Rongshun
authors.initials: R
authors.lastname: Wang
authors.forename: Shuwei
authors.initials: S
authors.lastname: Tang
authors.forename: Haitao
authors.initials: H
authors.lastname: Wang
authors.forename: Hao
authors.initials: H
authors.lastname: Sun