NO2和HSO反应的机理及动力学研究  

Study on the Atmospheric Reaction of NO2 with HSO:Mechanism and Kinetics

作　　者：吕陇梅 耿琳 文明杰 乔张宇 寇伟华 王琰 田少博 王睿[1] Lv Longmei;Geng Lin;Wen Mingjie;Qiao Zhangyu;Kou Weihua;Wang Yan;Tian Shaobo;Wang Rui(Shaanxi Key Laboratory of Catalysis,School of Chemical & Environment Science,Shaanxi University of Technology,Hanzhong 723000)

机构地区：[1]陕西理工大学化学与环境科学学院陕西省催化重点实验室

出　　处：《化学通报》2019年第6期534-541,503,482,共10页Chemistry

基　　金：陕西理工大学大学生创新创业训练计划项目(2017112)资助

摘　　要：本文采用CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ方法构建了NO2+HSO反应的单、三重态势能面,并对主通道速率常数进行了计算。结果表明,该反应在单[R1(HN(O)O+1SO)、R2(cis-HONO+1SO)和R3(trans-HONO+1SO)]、三重态[R6(HN(O)O+3SO)、R7(cis-HONO+SO^3)和R8(trans-HONO+3SO)]均存在3条抽氢反应通道,在单[R4(NO+HS(O)O)和R5(H+SO2+NO)]、三重态[R9(HS(O)O+NO)和R10(H+SO2+NO)]均存在两条抽氧通道,其中单重态抽氢通道R2(cis-HONO+1SO)是NO2+HSO反应主通道。利用传统过渡态理论(TST)并结合Wigner校正,计算了上述10条通道在200K^1000K温度范围内的速率常数。计算结果表明,NO2+HSO反应主通道在298K时的速率常数(7.78×10^-13cm^3·molecule^-1·s-1)与实验值(9.6×10^-12cm^3·molecule^-1·s^-1)相近。此外,水分子影响主通道R2(cis-HONO+1SO)经历了NO2+H2O…HSO和NO2+H2O…HSO(HSO+NO2…H2O)两条反应通道,且两条通道的能垒分别比R2升高了49.97和20.67 kcal·mol-1,说明在实际大气环境中水分子对NO2+HSO反应几乎没有影响。The mechanism for the reaction between NO2 and HSO was investigated at the CCSD(T)/aug-ccpVTZ//B3LYP/aug-cc-pVTZ level on both the singlet and triplet potential energy surfaces(PESs).The results showed that there are three hydrogen abstraction reaction channels on both singlet[R1 HN(O)O+1SO),R2(cis-HONO+1SO),and R3(trans-HONO+1SO)]and triplet[R6(HN(O)O+SO^3),R7(cis-HONO+3SO),and R8(trans-HONO+3SO)]PESs,as well as two oxygen abstraction reaction channels on both singlet[R4(NO+HS(O)O)and R5(H+SO2+NO)]and triplet[R9(HS(O)O+NO)and R10(H+SO2+NO)]on the triplet PESs.Among these channels,Channel R2(cis-HONO+1SO)on the singlet PESs is the favorable channel.The rate constants of above reaction channels were evaluated using classical transition state theory(TST)and Wigner correction.The calculated results showed that the reaction channel of cis-HONO+SO formations is favorable and its rate constant,at 298K,is 7.78×10^-13 cm3·molecule^-1·s^-1,which is in good agreement with experimental value(9.6×10^-12 cm^3·molecule^-1·s^-1).Water molecule catalyzed R2(cis-HONO+1SO)occurs through two different channels of NO2+H2O…HSO and NO2+H2O…HSO(HSO+NO2…H2O),where the barriers of the two channels respectively are enhanced by 49.97 kcal·mol^-1 and 20.67 kcal·mol^-1 than that of the naked reaction of R2,indicating that the effect of water molecules on the NO2+HSO reaction can be neglected in the actual atmospheric environment.

关 键 词：NO2 HSO 单与三重态势能面 反应机理 速率常数 

分 类 号：O643.12[理学—物理化学]