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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Combination Reactions of Propargyl Radical with Hydroxyl Radical and the Isomerization and Dissociation of trans-Propenal
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Combination Reactions of Propargyl Radical with Hydroxyl Radical and the Isomerization and Dissociation of trans-Propenal

机译：丙氨酸基团与羟基的组合反应及反式丙烯的异构化和解离

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Ab initio investigation for the ground-electronic potential energy surface (PES) of the CH2CCH + OH combination and the trans-CH2CHCHO isomerization and decomposition has been performed at the UCCSD(T)/CBS(TQ5)//M06-2X/aug-cc-pVTZ level of theory. Thermal and microcanonical rate constants, as well as branching ratios in the 300-2000 K temperature range have been predicted based on optimized structures and vibrational frequencies of species involved using statistical theoretical VRC-TST and RRKM master equation computations. The calculated results are in good agreement with the prior reported data, particularly as an accurate scaling of the energy barriers was carried out. Based on the view of PES and kinetic-predicted values, the reaction paths leading to C2H2 + CO + H-2, CH3CH + CO, C2H4 + CO, C2H3 + HCO, and C3H3O + H are the prevailing product channels for the C3H3 + OH bimolecular reaction under the considered 300-2000 K temperature range. Among those products, CH3CH + CO is the most dominant one in the low-temperature condition; however, C2H2 + CO + H-2 becomes the most favorable product in the high-temperature region. Alternatively, the C3H4O dissociation processes leading to C2H2 + CO + H-2, C2H3 + HCO, C2H4 + CO, and CH2C + CH2O constitute the major paths, in which, C2H2 + CO + H-2 is the most critical one with the similar to 62% and similar to 59% branching ratios at E = 148 and 182 kcal/mol, respectively. The overall second-order rate constants of the bimolecular reaction C3H3 + OH. products obtained at the pressure 760 Torr (Ar) can be illustrated by the modified Arrhenius expression of k(T) = 1.36 x 10(-13)T(1.26) exp[(-1.12 +/- 0.43 kcal mol(-1))/RT] and/or k(T) = 3.77 x 10(17)T(-7.58) exp[(-18.82 +/- 0.20 kcal mol(-1))/RT] cm(3) molecule(-1) s(-1), covering the temperature range of 300-1300 and/or 1300-2000 K, respectively. The total high-pressure limit rate constant for the C3H3 + OH -> CH2CCHOH barrierless processes is in good agreement with the k(T) = 8.30 x 10(-10) T-0.1 cm(3) molecule(-1) s(-1) literature data. Moreover, microcanonical rate constants for the C3H4O isomerization and dissociation are in excellent accordance with the previously predicted values given by Chin and Lee. The present study supplies a thorough insight into the mechanisms and kinetics of the C3H3 + OH combination as well as the C3H4O multistep isomerization/dissociation pathways.
机译：在UCCSD（T）/ CBS（TQ5）// M06-2X / AUG-中执行了CH2CCH + OH组合的地面电子电位能表面（PES）和转答CH2CHCHO异构化和分解的AB初始研究。 CC-PVTZ理论水平。基于使用统计理论VRC-TST和RRKM主级等式计算所涉及的物种的优化结构和振动频率，预测了300-2000K温度范围中的热和微胆速率常数。计算结果与先前的报告数据吻合良好，特别是作为能量屏障进行的准确缩放。基于PE和动力学预测值的视图，导致C 2 H 2 + CO + H-2，CH3CH + CO，C 2 H 4 + CO，C 2 H 3 + HCO和C3H30 + H的反应路径是C3H3 +的主要产品通道在考虑300-2000k的温度范围内哦双分子反应。在这些产品中，CH3CH + CO是低温条件中最占主导地位的CH3CH + CO;然而，C 2 H 2 + CO + H-2成为高温区域中最有利的产品。或者，导致C 2 H 2 + CO + H-2，C 2 H 3 + HCO，C 2 H 4 + CO和CH 2 C + CH 2 O的C3H 4 O离解方法构成了主要路径，其中C2H2 + CO + H-2是最关键的路径与E = 148和182kcal / mol的类似于62％且类似于59％的分支比率。双分子反应的总常数C3H3 + OH。在压力760托（AR）中获得的产品可以通过K（t）= 1.36×10（-13）℃（1.26）exp [（ - 1.12 +/- 0.43 kcal mol（-1） / r r]和/或k（t）= 3.77×10（17）T（-7.58）exp [（ - 18.82 +/- 0.20千瓦摩尔（-1））/ Rt] cm（3）分子（-1 ）S（-1），覆盖300-1300和/或1300-2000 k的温度范围。 C3H3 + OH - > CH2CCHOH障碍过程的总高压极限率常数与K（T）= 8.30×10（-10）T-0.1cm（3）分子（-1）S（ -1）文献数据。此外，C3H4O异构化和解离的微常规速率常数与由下巴和李给出的先前预测的值优异。本研究提供了彻底了解C3H3 + OH组合的机制和动力学以及C3H4O多步异构化/解离路径。

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