The reaction of Criegee intermediates with NO, RO2, and SO2, and their fate in the atmosphere
The reaction of Criegee intermediates with NO, RO2, and SO2, and their fate in the atmosphere
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DOI：
10.1039/c2cp42300f
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发表时间：
2012-01-01
影响因子：
3.3
通讯作者：
Novelli, A.
中科院分区：
文献类型：
--
作者：
Vereecken, L.;Harder, H.;Novelli, A.
首次用理论方法研究了Criegee中间体（CI）与NO和RO2自由基的反应，并重新考察了CI与SO2分子的反应. Cl与NO的反应被发现是缓慢的，具有明显的能垒。它们与RO2自由基的反应通过形成预反应性络合物进行，然后在浸没的屏障上在Cl碳上添加RO2自由基，导致更大的过氧自由基并打开与实验一致的低聚物形成的可能性。单重态双自由基的Cl与SO2的反应的影响进行检查，发现一个不同的反应机制相比，早期的工作。对于较大的CI，在大气压力下与SO2的反应主要产生热化的含硫次级臭氧化物。CI在大气中的命运进行了详细的研究，根据观测到的浓度在大气中的众多的共反应物，和估计的速率系数可从文献数据。SCI对流层化学的影响进行了讨论。
The reaction of Criegee intermediates (CI) with NO and RO2 radicals is studied for the first time by theoretical methodologies; additionally, the reaction of CI with SO2 molecules is re-examined. The reaction of CI with NO was found to be slow, with a distinct energy barrier. Their reaction with RO2 radicals proceeds by the formation of a pre-reactive complex followed by addition of the RO2 radical on the CI carbon over a submerged barrier, leading to a larger peroxy radical and opening the possibility for oligomer formation in agreement with experiment. The impact of singlet biradicals on the reaction of CI with SO2 is examined, finding a different reaction mechanism compared to earlier work. For larger CI, the reaction with SO2 at atmospheric pressures mainly yields thermalized sulfur-bearing secondary ozonides. The fate of the CI in the atmosphere is examined in detail, based on observed concentration of a multitude of coreactants in the atmosphere, and estimated rate coefficients available from literature data. The impact of SCI on tropospheric chemistry is discussed.