Theoretical study of the reactions of Criegee intermediates with ozone, alkylhydroperoxides, and carbon monoxide.
Theoretical study of the reactions of Criegee intermediates with ozone, alkylhydroperoxides, and carbon monoxide.
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DOI：
10.1039/c5cp03862f
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发表时间：
2015-09
期刊：
影响因子：
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通讯作者：
L. Vereecken;A. Rickard;M. Newland;W. Bloss
中科院分区：
文献类型：
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作者：
L. Vereecken;A. Rickard;M. Newland;W. Bloss
Criegee中间体（CI）与臭氧，O3的反应，已重新审查与更高层次的理论，根据早期的报告，O3可能是一个相关的汇的CI。更新后的速率系数表明，反应比最初预期的要慢一些，预计不会在对流层中发挥作用。在实验室条件下，Cl + O3反应可能很重要。发现Cl与ROOH中间体的反应通过预反应复合物进行，并且插入过程允许与最近的实验观察一致的低聚物的形成。Cl + ROOH反应还允许形成醚氧化物，其不与H2O反应，但可以氧化SO2。在对流层条件下，预期醚氧化物重新解离成Cl + ROOH络合物，并最终遵循插入反应形成较长链的氢过氧化物。预计Cl + ROOH反应不会在大气中发挥重要作用。CI与CO分子的反应在非常高的理论水平上进行了研究，但没有发现能量上可行的路线，导致非常低的速率系数。这些结果进行了比较，对大量的文献综述的实验数据。
The reaction of Criegee intermediates (CI) with ozone, O3, has been re-examined with higher levels of theory, following earlier reports that O3 could be a relevant sink of CI. The updated rate coefficients indicate that the reaction is somewhat slower than originally anticipated, and is not expected to play a role in the troposphere. In experimental (laboratory) conditions, the CI + O3 reaction can be important. The reaction of CI with ROOH intermediates is found to proceed through a pre-reactive complex, and the insertion process allows for the formation of oligomers in agreement with recent experimental observations. The CI + ROOH reaction also allows for the formation of ether oxides, which don't react with H2O but can oxidize SO2. Under tropospheric conditions, the ether oxides are expected to re-dissociate to the CI + ROOH complex, and ultimately follow the insertion reaction forming a longer-chain hydroperoxide. The CI + ROOH reaction is not expected to play a significant role in the atmosphere. The reaction of CI with CO molecules was studied at very high levels of theory, but no energetically viable route was found, leading to very low rate coefficients. These results are compared against an extensive literature overview of experimental data.