Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Renmin Road 5268, Changchun, Jilin 130024, PR China.
Ningxia Entry-Exit Inspection and Quarantine Bureau, Yinchuan, Ningxia 750001, PR China.
J Mol Graph Model. 2014 Mar;48:18-27. doi: 10.1016/j.jmgm.2013.09.003. Epub 2013 Sep 16.
Potential energy surface for the reaction of hydroxyl radical (OH) with 3-fluoropropene (CH₂CHCH₂F) has been studied to evaluate the reaction mechanisms, possible products and rate constants. It has been shown that the CH₂CHCH₂F with OH reaction takes place via a barrierless addition/elimination and hydrogen abstraction mechanism. It is revealed for the first time that the initial step for the barrierless additional process involves a pre-reactive loosely bound complex (CR1) that is 1.60 kcal/mol below the energy of the reactants. Subsequently, the reaction bifurcates into two different pathways to form IM1 (CH₂CHOHCH₂F) and IM2 (CH₂OHCHCH₂F), which can decompose or isomerize to various products via complicated mechanisms. Variational transition state model and multichannel RRKM theory are employed to calculate the temperature-, pressure-dependent rate constants and branching ratios. At atmospheric pressure with He as bath gas, IM1 formed by collisional stabilization is dominated at T≤600 K; whereas the direct hydrogen abstraction leading to CH₂CHCHF and H₂O are the major products at temperatures between 600 and 3000 K, with estimated contribution of 72.9% at 1000 K. Furthermore, the predicted rate constants are in good agreement with the available experimental values.
羟基自由基（OH）与 3-氟丙烯（CH₂CHCH₂F）反应的势能面已经过研究，以评估反应机制、可能的产物和速率常数。研究表明，CH₂CHCH₂F 与 OH 的反应通过无势垒加成/消除和氢提取机制进行。首次揭示了无势垒加成过程的初始步骤涉及一个预反应的松散结合复合物（CR1），其能量比反应物低 1.60 kcal/mol。随后，反应分叉成两条不同的途径，形成 IM1（CH₂CHOHCH₂F）和 IM2（CH₂OHCHCH₂F），它们可以通过复杂的机制分解或异构化为各种产物。变分过渡态模型和多通道 RRKM 理论用于计算温度、压力依赖的速率常数和分支比。在大气压下，以 He 为浴气，通过碰撞稳定化形成的 IM1 在 T≤600 K 时占主导地位；而在 600 至 3000 K 的温度范围内，直接氢提取导致 CH₂CHCHF 和 H₂O 是主要产物，在 1000 K 时估计贡献为 72.9%。此外，预测的速率常数与可用的实验值吻合良好。
