【作者】 张琬峤； 唐树伟； 孙昊；

【Author】 Wanqiao Zhang;Shuwei Tang;Hao Sun;Department of Chemistry, Northeast Normal University;

【机构】 东北师范大学；

【摘要】 反式-2-氯乙烯基二氯胂是一战中生产的一种化学战剂。量子化学理论方法对于计算高毒性反应是一种精确而且安全的研究方法。本文运用密度泛函理论研究了气相下二氧化氮和路易氏剂的反应。反应物,产物和过渡态等构型运用B3LYP/6-311+g(d,p)方法计算得来。单点能计算使用MP2,G3和CCSD(T)方法。反应通过两种反应机理进行,分别为氢提取和C-加成/消除机理。运用RRKM理论计算反应速率常数,结果表明加成消除机理在低温条件下优于氢提取反应通道。更多还原

【Abstract】 The trans-2-chlorovinyldichloroarsine(Lewisite) was produced during WWI as chemical warfare agents. 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 nitrogen dioxide with Lewisite were studied by the density functional theory. The geometries of reactants, products and transition states were optimized at the B3LYP/6-311+g(d,p) level. The single-point energies were calculated using MP2, G3 and CCSD(T) method. This reaction exhibited two mechanisms, namely, direct hydrogen abstraction and C-addition/elimination. Multichannel RRKM 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.更多还原