| 王竹青,张勇奇,田汾奕,文明杰.化学通报,2019,82(7):649-654. |
| HO2 + HONO及其异构体抽氢反应机理 |
| Hydrogen abstraction reaction for the mechanism of HO2 with HONO and its isomers |
| 投稿时间：2019-02-20 修订日期：2019-04-16 |
| DOI： |
| 中文关键词: HONO HO2 反应机理 速率常数 |
| 英文关键词:HONO, HO2, Reactions Mechanism, Rate constant |
| 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 |
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| 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. |
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