| 吕陇梅,耿琳,文明杰,乔张宇,寇伟华,王琰,田少博,王睿.化学通报,2019,82(6):534-541,503. |
| NO2和HSO反应的反应机理及动力学研究 |
| Study on the Atmospheric Reaction of NO2 with HSO: Mechanism and Kinetics |
| 投稿时间：2018-10-16 修订日期：2019-03-12 |
| DOI： |
| 中文关键词: NO2 HSO 单、三重态势能面 反应机理 速率常数 |
| 英文关键词:NO2 HSO Singlet and Triplet PESs Reaction mechanism Rate constant |
| 基金项目:陕西理工大学大学生创新创业训练计划项目（2017112） |
|
| 摘要点击次数: 1835 |
| 全文下载次数: 0 |
| 中文摘要: |
| 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。研究结果表明，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 + 3SO)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200 ~ 1000 K温度范围内的速率常数。计算结果表明，NO2 + HSO反应主通道在298 K时的速率常数(7.78×10-13cm3?molecule-1?s-1)与实验值(9.6×10-12 cm3?molecule-1?s-1)相吻合。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20.43 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。 |
| 英文摘要: |
| The mechanism for the reaction between NO2 and HSO is investigated at the CCSD(T)/aug-cc-pVTZ //B3LYP/aug-cc-pVTZ level on both the singlet and triplet potential energy surfaces (PESs). The results show 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 + 3SO), 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 show that the reaction channel of cis-HONO + SO formations is favorable and its rate constant, at 298 K, is 7.78×10-13 cm3?molecule-1?s-1, which is good agreement with experimental value (9.6×10-12 cm3?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 barrier of the two channels respectively enhance by 49.97 and 20.43kcal?mol-1than that of the naked reaction of R2, indicating that the effect of water molecules on the NO2 + HSO reaction can be neglect in the actual atmospheric environment. |
| 查看全文 查看/发表评论 下载PDF阅读器 |
| 关闭 |
|
|
|