Theoretical and experimental study of the OH radical reaction with HCN
Theoretical and experimental study of the OH radical reaction with HCN
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DOI：
10.1080/00268976.2013.802036
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发表时间：
2013-07-01
影响因子：
1.7
通讯作者：
Nielsen, Claus J.
中科院分区：
文献类型：
--
作者：
Bunkan, Arne Joakim C.;Liang, Chi-Hsiu;Nielsen, Claus J.
通过长光程 FTIR 光谱法，在 298 +/- 2K 和 1013 +/- 10 hPa 的纯化空气中测量了 OH 与 (HCN)-C-13 和 (HCN)-N-15 的反应速率相对于与 (HCN)-C-12-N-14 的反应速率； C-12/C-13 和 N-14/N-15 动力学同位素效应分别确定为 0.9733 +/- 0.0012 和 0.9840 +/- 0.0016 (1 sigma)。通过量子化学方法研究了反应的基态势能超表面，根据该方法，HCN + OH反应通过将OH添加到势垒高度为15.4 kJ mol(-1)的碳原子上进行。反应速率系数和动力学同位素效应的主方程模型与实验结果吻合良好。
The reaction rates of OH with (HCN)-C-13 and (HCN)-N-15 have been measured relative to that with (HCN)-C-12-N-14 at 298 +/- 2K and 1013 +/- 10 hPa in purified air by long-path FTIR spectroscopy; the C-12/C-13 and N-14/N-15 kinetic isotope effects were determined to be 0.9733 +/- 0.0012 and 0.9840 +/- 0.0016 (1 sigma), respectively. Ground-state potential energy hyper-surfaces of the reaction were investigated by quantum chemistry methods according to which the HCN + OH reaction proceeds via addition of OH to the carbon atom with a barrier height of 15.4 kJ mol(-1). Master equation modelling of the reaction rate coefficient and kinetic isotope effects show good agreement with the experiments.