Multichannel reaction of C2Cl3 + O2 studied by time-resolved Fourier transform infrared emission spectroscopy.
Multichannel reaction of C2Cl3 + O2 studied by time-resolved Fourier transform infrared emission spectroscopy.
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DOI：
10.1021/jp074058c
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发表时间：
2007-08
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影响因子：
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通讯作者：
Tiancheng Xiang;Kunhui Liu;Shaolei Zhao;Hongmei Su;F. Kong;Baoshan Wang
中科院分区：
文献类型：
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作者：
Tiancheng Xiang;Kunhui Liu;Shaolei Zhao;Hongmei Su;F. Kong;Baoshan Wang
用阶跃扫描时间分辨傅里叶变换红外发射光谱研究了C(2)Cl(3)自由基与O(2)的多通道反应。观察到了Cl(2)CO、CO和CO(2)的振动激发产物，确定了形成ClCO+Cl(2)CO、CO+CCl(3)O和CO(2)+CCl(3)的三个主要反应通道。通过光谱拟合得到了产物CO的振动态分布，确定了CO的初生平均振动能为59.9kJ/mol。结果表明，实验测得的CO振动能远大于统计模型的预测值。结合前人的从头计算结果，非统计动力学和机理被表征为通过包括过氧基中间体C(2)Cl(3)OO*和关键的三元环COO中间体的短寿命反应中间体的无障碍加成-消除反应。
The multichannel reaction of the C(2)Cl(3) radical with O(2) has been studied thoroughly by step-scan time-resolved Fourier transform infrared emission spectroscopy. Vibrationally excited products of Cl(2)CO, CO, and CO(2) are observed and three major reaction channels forming respectively ClCO + Cl(2)CO, CO + CCl(3)O, and CO(2) + CCl(3) are identified. The vibrational state distribution of the product CO is derived from the spectral fitting, and the nascent average vibrational energy of CO is determined to be 59.9 kJ/mol. A surprisal analysis is applied to evaluate the vibrational energy disposal, which reveals that the experimentally measured CO vibrational energy is much more than that predicted by statistical model. Combining previous ab initio calculation results, the nonstatistical dynamics and mechanism are characterized to be barrierless addition-elimination via short-lived reaction intermediates including the peroxy intermediate C(2)Cl(3)OO* and a crucial three-member-ring COO intermediate.