Enhanced Mobility during Diels–Alder Reaction: Results of Molecular Simulations
Enhanced Mobility during Diels–Alder Reaction: Results of Molecular Simulations
复制标题
Diels-Alder 反应过程中的迁移率增强：分子模拟结果
DOI：
10.1021/acs.jpclett.2c00886
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Leitner, David M.
中科院分区：
文献类型：
--
作者：
Reid, Korey M.;Leitner, David M.
最近的测量表明，狄尔斯-阿尔德 (DA) 和其他常见化学反应期间溶剂分子的流动性增强。我们展示了在实验研究的反应物浓度下，糠胺和马来酰亚胺在乙腈中的 DA 环加成反应最后阶段（从过渡态构型到产物）的分子动力学模拟结果。我们发现，在数百皮秒内，溶剂和反应物分子的移动性增强，距离 DA 产品至少达到一纳米。模拟中观察到的迁移率增强的因素排除了局部加热，而是发现这是由于 DA 产物形成后溶剂松弛所致。
Recent measurements indicate enhanced mobility of solvent molecules during Diels–Alder (DA) and other common chemical reactions. We present results of molecular dynamics simulations of the last stages of the DA cycloaddition reaction, from the transition state configuration to product, of furfurylamine and maleimide in acetonitrile at reactant concentrations studied experimentally. We find enhanced mobility of solvent and reactant molecules up to at least a nanometer from the DA product over hundreds of picoseconds. Local heating is ruled out as a factor in the enhanced mobility observed in the simulations, which is instead found to be due to solvent relaxation following the formation of the DA product.