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环戊烯臭氧化反应瞬变物种产生机制

杨晓璐 徐义生 郭学超 郭 创 陈建华 邓建国

杨晓璐, 徐义生, 郭学超, 郭 创, 陈建华, 邓建国. 环戊烯臭氧化反应瞬变物种产生机制[J]. 环境科学研究, 2014, 27(12): 1440-1449.
引用本文: 杨晓璐, 徐义生, 郭学超, 郭 创, 陈建华, 邓建国. 环戊烯臭氧化反应瞬变物种产生机制[J]. 环境科学研究, 2014, 27(12): 1440-1449.
YANG Xiao-lu, XU Yi-sheng, GUO Xue-chao, GUO Chuang, CHEN Jian-hua, DENG Jian-guo. Theoretical and Experimental Study of the Formation Mechanism of Transient Species in the Ozonolysis of Cyclopentene[J]. Research of Environmental Sciences, 2014, 27(12): 1440-1449.
Citation: YANG Xiao-lu, XU Yi-sheng, GUO Xue-chao, GUO Chuang, CHEN Jian-hua, DENG Jian-guo. Theoretical and Experimental Study of the Formation Mechanism of Transient Species in the Ozonolysis of Cyclopentene[J]. Research of Environmental Sciences, 2014, 27(12): 1440-1449.

环戊烯臭氧化反应瞬变物种产生机制

基金项目: 国家自然科学基金面上项目(40975073,41375133)

Theoretical and Experimental Study of the Formation Mechanism of Transient Species in the Ozonolysis of Cyclopentene

  • 摘要: 大气中烯烃臭氧化反应产物是二次有机气溶胶(SOA)形成的重要前体物. 运用自行组建的低温基质隔离系统研究环戊烯臭氧化反应的瞬变物种产生机制. 采用程序升温方法,将温度从6 K升至115 K,用傅里叶红外光谱仪检测不同温度下生成的活性中间体,并将试验值与理论计算值、文献报道值进行对比,以确定中间体构型. 结果表明:环戊烯臭氧化反应生成的中间体——POZ(初级臭氧化物)、SOZ(二次臭氧化物)和CI(一分子羰基氧化物和一分子醛或酮)被成功检测到. 其中,POZ的特征吸收峰在705和946 cm-1处,对应O—O—O反对称伸缩振动和环变形振动;SOZ特征吸收峰在939 cm-1处,对应C—O伸缩振动;CI的特征吸收峰在1 733和853 cm-1处,分别对应CO伸缩振动和O—O伸缩振动. 据此,环戊烯臭氧化反应遵循Criegee机制. 采用4种量子化学计算方法——B3LYP/6-311++G(d,2p)、B3LYP/6-311++G(3df,3pd)、MP2/aug-cc-pvdz和PW91PW91/6-311++G(3df,3pd),计算POZ、SOZ和CI特征吸收峰的振动频率,其中POZ在705 cm-1处吸收峰的振动频率计算值分别为725、698、703、680 cm-1;SOZ在1 030 cm-1处吸收峰的振动频率计算值分别为1 017、1 018、1 025和993 cm-1;CI在1 733 cm-1处吸收峰的振动频率计算值分别为1 796、1 803、1 732和1 745 cm-1.表明MP2/aug-cc-pvdz计算的特征振动频率与试验值最接近.

     

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出版历程
  • 收稿日期:  2014-01-22
  • 修回日期:  2014-06-23
  • 刊出日期:  2014-12-25

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