• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The Journal of Chemical Physics >Dynamics of the reactions of O(~1D) with CD_ 3OH and CH_ 3OD studied with time-resolved Fourier-transform IR spectroscopy
【24h】

Dynamics of the reactions of O(~1D) with CD_ 3OH and CH_ 3OD studied with time-resolved Fourier-transform IR spectroscopy

机译：时间分辨傅里叶变换红外光谱研究O（〜1D）与CD_3OH和CH_ 3OD的反应动力学

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

We investigated the reactivity of O(~1D) towards two types of hydrogen atoms in CH_ 3OH. The reaction was initiated on irradiation of a flowing mixture of O_ 3 and CD_ 3OH or CH_ 3OD at 248 nm. Relative vibration-rotational populations of OH and OD (1 ≤ v ≤ 4) states were determined from their infrared emission recorded with a step-scan time-resolved Fourier-transform spectrometer. In O(~1D) CD_ 3OH, the rotational distribution of OD is nearly Boltzmann, whereas that of OH is bimodal; the product ratio OHOD is 1.56 ± 0.36. In O(~1D) CH_ 3OD, the rotational distribution of OH is nearly Boltzmann, whereas that of OD is bimodal; the product ratio OHOD is 0.59 ± 0.14. Quantum-chemical calculations of the potential energy and microcanonical rate coefficients of various channels indicate that the abstraction channels are unimportant and O(~1D) inserts into the C-H and O-H bonds of CH_ 3OH to form HOCH_ 2OH and CH_ 3OOH, respectively. The observed three channels of OH are consistent with those produced via decomposition of the newly formed OH or the original OH moiety in HOCH_ 2OH or decomposition of CH_ 3OOH. The former decomposition channel of HOCH_ 2OH produces vibrationally more excited OH because of incomplete intramolecular vibrational relaxation, and decomposition of CH_ 3COOH produces OH with greater rotational excitation, likely due to a large torque angle during dissociation. The predicted OHOD ratios are 1.31 and 0.61 for O(~1D) CD_ 3OH and CH_ 3OD, respectively, at collision energy of 26 kJ mol~ (-1), in satisfactory agreement with the experimental results. These predicted product ratios vary weakly with collision energy.
机译：我们研究了O（〜1D）对CH_3OH中两种氢原子的反应性。通过在248nm下照射流动的O 3和CD 3 OH或CH 3 OD的混合物来引发反应。 OH和OD（1≤v≤4）态的相对振动-旋转种群是由阶跃扫描时间分辨傅里叶变换光谱仪记录的红外发射确定的。在O（〜1D）CD_3OH中，OD的旋转分布接近玻尔兹曼，而OH的旋转分布为双峰。产物比率OHOD为1.56±0.36。在O（〜1D）CH_ 3OD中，OH的旋转分布几乎是玻耳兹曼，而OD的旋转分布是双峰的。产物比率OHOD为0.59±0.14。各种通道的势能和微规范速率系数的量子化学计算表明，抽象通道并不重要，O（〜1D）插入CH_ 3OH的C-H和O-H键分别形成HOCH_2OH和CH_3OOH。观察到的OH的三个通道与通过分解新形成的OH或HOCH_2OH中的原始OH部分或CH_3OOH分解产生的通道一致。由于分子内的振动弛豫不完全，HOCH_2OH的前一个分解通道产生了更多的振动激发的OH，而CH_3COOH的分解产生了具有更大旋转激发的OH，这可能是由于解离过程中的大扭矩角所致。在碰撞能量为26 kJ mol〜（-1）时，O（〜1D）CD_3OH和CH_ 3OD的预测OHOD比分别为1.31和0.61。与实验结果令人满意。这些预测的产品比率随碰撞能量的变化很小。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号