论文标题
DIELS-ALDER型反应的反应性原子模拟：2,3-二溴豆位二烯自由基与甲基氢化物的构象和动态效应
Reactive atomistic simulations of Diels-Alder-type reactions: Conformational and dynamic effects in the polar cycloaddition of 2,3-dibromobutadiene radical ions with maleic anhydride
论文作者
论文摘要
已经研究了理论上使用多表象绝经性反应性分子动力学研究了理论上研究了马利甲基离子甲基离子甲基离子甲基离子甲基离子（极性环节）的动力学，动力学和构象特异性。发现了一致和逐步反应途径的竞争，二烯的S-CIS和S-Trans构象体都是反应性的。对反应的最小动态路径的分析表明，反应物分子的旋转和振动对于将系统推向过渡态都很重要。将价格计算为$ k = 5.1 \ times 10^{ - 14} $ s $^{ - 1} $的s-cis $，$ k = 3.8 \ times 10^{ - 14} $ s $ s $ s $^{ - 1} $用于2,3- dibibromobutadiene的S-S-Trans构量在300 k的内部温度下仅适用于300 K.发现二烯的Gauche构象异构体经历了旋转激发驱动的较慢，一致且大多是同步反应。此处介绍的结果为详细的实验研究提供了有关气相在单碰撞条件下极性环加成的动力学的详细实验研究。
The kinetics, dynamics and conformational specificities for the ionic Diels-Alder reaction (polar cycloaddition) of maleic anhydride with 2,3-dibromobutadiene radical ions have been studied theoretically using multisurface adiabatic reactive molecular dynamics. A competition of concerted and stepwise reaction pathways was found and both the s-cis and s-trans conformers of of the diene are reactive. The analysis of the minimum dynamic path of the reaction indicates that both, rotations and vibrations of the reactant molecules are important for driving the system towards the transition state. The rates were computed as $k = 5.1 \times 10^{-14}$ s$^{-1}$ for the s-cis and $k = 3.8 \times 10^{-14}$ s$^{-1}$ for the s-trans conformer of 2,3-dibromobutadiene at an internal temperature of 300 K. The present results are to be contrasted with the neutral variant of the title system in which only the gauche conformer of the diene was found to undergo a considerably slower, concerted and mostly synchronous reaction driven by the excitation of rotations. The results presented here inform detailed experimental studies of the dynamics of polar cycloadditions under single-collision conditions in the gas phase.
