J Environ Sci (China). 2014 Jan 1;26(1):181-8. doi: 10.1016/s1001-0742(13)60396-4.
The ozonolysis of 2,3,7,8-tetra-chlorodibenzo-p-dioxin (2,3,7,8-TCDD) is an efficient degradation way in the atmosphere. The ozonolysis process and possible reactions path of Criegee Intermediates with NO and H2O are introduced in detail at the method of MPWB1K/6-31+G(d,p)//MPWB1K/6-311+G(3df,2p) level. In ozonolysis, H2O is an important source of OH radical formation and initiated the subsequent degradation reaction. The Rice-Ramsperger-Kassel-Marcus (RRKM) theory was applied to calculate rate constants with the temperature ranging from 200 to 600 K. The rate constant of reaction between 2,3,7,8-TCDD and O3 is 4.80 x 10(-20) cm3/(mole x sec) at 298 K and 760 Torr. The atmospheric lifetime of the reaction species was estimated according to rate constants, which is helpful for the atmospheric model study on the degradation and risk assessment of dioxin.
臭氧氧化 2,3,7,8-四氯二苯并对二恶英（2,3,7,8-TCDD）是大气中一种有效的降解途径。本文在 MPWB1K/6-31+G(d,p)//MPWB1K/6-311+G(3df,2p)水平上详细介绍了 Criegee 中间体与 NO 和 H2O 的臭氧氧化过程和可能的反应途径。在臭氧氧化中，H2O 是 OH 自由基形成的重要来源，并引发了随后的降解反应。应用 Rice-Ramsperger-Kassel-Marcus（RRKM）理论计算了 200 至 600 K 温度范围内的速率常数。在 298 K 和 760 Torr 下，2,3,7,8-TCDD 与 O3 之间的反应速率常数为 4.80 x 10(-20) cm3/(mole x sec)。根据速率常数估算了反应物种的大气寿命，这有助于大气模型对二恶英降解和风险评估的研究。
