Temperature effects on the branching dynamics in the model ambimodal (6 + 4)/(4 + 2) intramolecular cycloaddition reaction,Journal of Computational Chemistry

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Temperature effects on the branching dynamics in the model ambimodal (6 + 4)/(4 + 2) intramolecular cycloaddition reaction
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2024-08-21 , DOI: 10.1002/jcc.27484
Tatsuhiro Murakami _{1,

2} , Daiki Hayashi ₁ , Yuya Kikuma ₁ , Keita Yamaki ₁ , Toshiyuki Takayanagi ₁

Affiliation

C₁₄H₂₀ (tetradecapentaene) is a simple model system exhibiting post transition-state behavior, wherein both the (6 + 4) and (4 + 2) cycloaddition products are formed from one ambimocal transition state structure. We studied the bifurcation dynamics starting from the two ambimodal transition state structures, the chair-form and boat-form, using the quasi-classical trajectory, classical molecular dynamics, and ring-polymer molecular dynamics methods on the parameter-optimized semiempirical GFN2-xTB potential energy surface. It was found that the calculated branching fractions differ between the chair-form and boat-form due to the different nature in the IRC pathways. We also investigated the effects of temperature on bifurcation dynamics and found that, at higher temperatures, trajectories stay longer in the intermediate region of the potential energy surface.

中文翻译：

温度对模型双峰（6 + 4）/（4 + 2）分子内环加成反应中支化动力学的影响

C₁₄H₂₀ （tetradecapentaene）是一种简单的模型系统，表现出后过渡态行为，其中（6 + 4）和（4 + 2）环加成产物均由一种模棱两可的过渡态结构形成。我们在参数优化的半经验 GFN2-xTB 势能面上使用准经典轨迹、经典分子动力学和环形聚合物分子动力学方法，研究了从椅子型和船型两种双峰过渡态结构开始的分叉动力学。发现由于 IRC 通路的性质不同，计算出的分支分数在 chair 型和 boat-form 之间不同。我们还研究了温度对分岔动力学的影响，发现在较高温度下，轨迹在势能表面的中间区域停留的时间更长。

更新日期：2024-08-21

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