Comparison of classical reaction paths and tunneling paths studied with the semiclassical instanton theory.
Comparison of classical reaction paths and tunneling paths studied with the semiclassical instanton theory.
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经典反应路径与半经典瞬子理论研究的隧道路径的比较。
DOI：
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发表时间：
2017
期刊：
影响因子：
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通讯作者：
J. Kästner
中科院分区：
文献类型：
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作者：
J. Meisner;M. N. Markmeyer;Matthias U Bohner;J. Kästner
利用瞬子理论研究了2，4，6-三叔丁基苯基自由基向3，5-二叔丁基苯酚的氢原子转移反应中的原子隧道效应，该反应具有短但强烈弯曲的反应路径。我们发现隧穿路径从经典的内在反应坐标，质量加权笛卡尔坐标中的最陡下降路径定性偏离。为了进行比较，我们实现了一个新的变体的预测-校正算法的计算的内在反应坐标。我们使用的反作用力分析方法作为一种手段，分解成结构和电子元件的反应势垒。由于窄的能垒，原子隧穿在上述反应中是重要的，甚至在室温以上。我们计算的速率常数在350 K和100 K之间与实验值吻合得很好。我们发现在100 K时H/D动力学同位素效应接近106。在400 K以下，氚的迁移主要是由钍引起的，而在300 K以下，氘的迁移主要是由钍引起的.我们比较了HCl + Cl反应中氢原子转移的隧穿路径和经典路径的长度，并对该反应中的切角进行了量化。在低温下，隧穿路径比经典路径短约40%。
Atom tunneling in the hydrogen atom transfer reaction of the 2,4,6-tri-tert-butylphenyl radical to 3,5-di-tert-butylneophyl, which has a short but strongly curved reaction path, was investigated using instanton theory. We found the tunneling path to deviate qualitatively from the classical intrinsic reaction coordinate, the steepest-descent path in mass-weighted Cartesian coordinates. To perform that comparison, we implemented a new variant of the predictor-corrector algorithm for the calculation of the intrinsic reaction coordinate. We used the reaction force analysis method as a means to decompose the reaction barrier into structural and electronic components. Due to the narrow energy barrier, atom tunneling is important in the abovementioned reaction, even above room temperature. Our calculated rate constants between 350 K and 100 K agree well with experimental values. We found a H/D kinetic isotope effect of almost 106 at 100 K. Tunneling dominates the protium transfer below 400 K and the deuterium transfer below 300 K. We compared the lengths of the tunneling path and the classical path for the hydrogen atom transfer in the reaction HCl + Cl and quantified the corner cutting in this reaction. At low temperature, the tunneling path is about 40% shorter than the classical path.
影响因子：
62.1
作者：
Layfield, Joshua P.;Hammes-Schiffer, Sharon
通讯作者：
Hammes-Schiffer, Sharon
影响因子：
2.9
作者：
Kaestner, Johannes;Carr, Joanne M.;Sherwood, Paul
通讯作者：
Sherwood, Paul
影响因子：
56.9
作者：
Schreiner, Peter R.;Reisenauer, Hans Peter;Allen, Wesley D.
通讯作者：
Allen, Wesley D.