中文关键词:HONOHO₂反应机理速率常数 英文关键词:HONO, HO₂, ReactionsMechanism, Rateconstant 基金项目:四川省教育厅理科重点项目，17ZA0276；四川理工学院人才引进项目，2016RCL17

作者	单位	E-mail
王竹青	四川轻化工大学	wangzq128@163.com
张勇奇	陕西理工大学
田汾奕	陕西理工大学
文明杰	陕西理工大学

摘要点击次数:1251 全文下载次数:0 中文摘要: 本文在CCSD(T)/aug-cc-pVTZ//M06-2X/6-311+G(3d,2p)水平上构建了HO₂与HONO及其异构体的反应势能剖面,并对各通道的速率常数进行了计算。结果表明,HONO存在cis-HONO、trans-HONO、HNO₂三种不同的异构体,其中HNO₂是最稳定的构型。HNO₂+ HO₂反应能垒(R3)比其他两个反应(R1(cis-HONO + HO₂)和R2(trans-HONO + HO₂))的能垒降低了8.2 ~ 13.8 kcal.mol^_-1。采用传统过渡态理论结合Wigner校正对各反应在240 K ~ 425 K温度范围内的速率常数进行了计算。结果表明,反应R3(HNO₂+ HO₂)的速率常数比R1(cis-HONO + HO₂)和R2(trans-HONO + HO₂)的对应值大了4 ~ 9个数量级,表明HO₂ + HONO及其异构体的抽氢反应的速率主要取决于HNO₂+ HO₂反应。 英文摘要: The mechanism for the reaction of HO₂ with HONO and its isomers was investigated at the CCSD(T)/aug-cc-pVTZ//M06-2X/6-311+G(3d,2p) level. The results show that HONO has three different isomers, labeled as cis-HONO, trans-HONO and HNO₂, where HNO₂ is the most stable in the three isomers. The energy barrier of HO₂ + HNO₂ is lower by 8.2 – 13.8 kcal?mol^_-1 than that of the other two reactions of cis-HONO + HO₂and trans-HONO + HO₂. The rate constants of the three reactions were calculated by the traditional transition state theory with Wigner correction in the temperature range of 240 K-425 K. The calculated results show that the constant of HO₂ +HNO₂reaction is larger by 4 - 9 orders of magnitude than those of cis-HONO + HO₂and trans-HONO + HO₂, indicates that the total rate constants for the reaction of HO₂ with HONO and its isomers mainly lie on the contribution of HO₂ + HNO₂reaction. 查看全文查看/发表评论下载PDF阅读器 相关附件：版权转让声明书版权转让声明书 -->