Radical–Radical Reaction Dynamics Probed Using Millimeterwave Spectroscopy: Propargyl + NH 2 /ND 2
Radical–Radical Reaction Dynamics Probed Using Millimeterwave Spectroscopy: Propargyl + NH 2 /ND 2
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使用毫米波光谱探测自由基 - 自由基反应动力学：丙炔 NH 2 /ND 2
DOI：
10.1021/acs.jpclett.1c03813
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Suits, Arthur G.
中科院分区：
文献类型：
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作者：
Gurusinghe, Ranil M.;Dias, Nureshan;Mebel, Alexander M.;Suits, Arthur G.
我们应用啁啾脉冲均匀流毫米波（CPUF-mmW）光谱研究炔丙基和氨基自由基（C3 H3 + NH 2/ND 2）之间的反应，自由基-自由基反应的重要性，在气相化学的天体化学环境和燃烧系统的复杂的多通道反应动力学。允许光解产生的自由基在良好表征的准均匀超音速流中反应，并且mmW旋转光谱（70-93 GHz）用于同时检测反应产物：HCN、HNC、HC 3 N、DCN、DNC和DC 3 N，而测量的纯旋转线的光谱强度允许量化产物分支。高层次的电子结构计算用于理论预测的反应途径和分支。实验推导出的产品支化分数进行了比较，从统计模拟的RRKM理论的基础上的结果。产物支化被认为是强烈依赖于C3 H3和NH 2/ND 2反应物的过剩内能。
We apply chirped-pulse uniform flow millimeterwave (CPUF-mmW) spectroscopy to study the complex multichannel reaction dynamics in the reaction between the propargyl and amino radicals (C3H3+ NH2/ND2), a radical–radical reaction of importance in the gas-phase chemistry of astrochemical environments and combustion systems. The photolytically generated radicals are allowed to react in a well-characterized quasi-uniform supersonic flow, and mmW rotational spectroscopy (70–93 GHz) is used for simultaneous detection of the reaction products: HCN, HNC, HC3N, DCN, DNC, and DC3N, while spectral intensities of the measured pure-rotational lines allow product branching to be quantified. High-level electronic structure calculations were used for theoretical prediction of the reaction pathways and branching. Experimentally deduced product branching fractions were compared with the results from statistical simulations based on the RRKM theory. Product branching was found to be strongly dependent on the excess internal energy of the C3H3and NH2/ND2reactants.