文献类型：期刊文献

中文题名：电子结构视角下的定向外部电场对Diels–Alder反应调控机理

英文题名：Electronic structure insights into oriented external electric field effects on Diels-Alder reaction

作者：廖俊超[1];黄伟杰[1];徐小飞[1];唐伟强[1];赵双良[2]

机构：[1]华东理工大学化工学院,上海200237;[2]广西大学化学与化工学院,广西低碳技术与绿色化工材料实验室,南宁530004

年份：2025

卷号：43

期号：21

起止页码：102

中文期刊名：科技导报

外文期刊名：Science & Technology Review

收录：;北大核心:【北大核心2023】；

基金：国家自然科学基金青年科学基金项目(22108070);中国科协青年人才托举工程(2022QNRC001)。

语种：中文

中文关键词：计算化学;定向外部电场;Kohn-Sham密度泛函;Diels-Alder反应

外文关键词：computational chemistry;oriented external electric field;Kohn?Sham density functional theory;Diels?Alder reaction

摘要：基于Kohn-Sham密度泛函理论,以环戊二烯与甲基乙烯基酮的Diels-Alder反应为例,揭示了定向外部电场(OEEF)对Diels-Alder反应的调控机制及微观机理。结果表明,电场方向和强度(F_(Z))对反应速率与选择性均有显著影响:F_(Z)>0时反应速率增加、内型产物占比上升;F_(Z)<0时反应速率降低,但有利于提高外型产物的选择性。微观机制分析显示,OEEF通过诱导电子极化、降低HOMOCP-LUMOMVK能隙,进而提高分子轨道间的电子迁移能力,增强过渡态成键原子间的相互作用并促进片段间电荷转移,从而稳定过渡态并降低能垒。此外,给出了OEEF调控反应的静电势、电子密度差、轨道能隙、片段电荷与偶极变化等电子结构描述符,借助这些描述符可理解和预测OEEF对Diels-Alder反应的影响。
Using Kohn–Sham density functional theory,we investigate the Diels–Alder reaction between cyclopentadiene and methyl vinyl ketone as a model system to elucidate the regulatory mechanism and microscopic origin of oriented external electric fields(OEEF)on cycloaddition reactivity.The results demonstrate that both the direction and magnitude(F_(Z))of the electric field significantly affect the reaction rate and selectivity:When F_(Z)>0,the reaction rate accelerates and the endo product ratio increases,whereas F_(Z)<0 leads to a slower reaction but favors exo product selectivity.Mechanistic analysis reveals that OEEF induces electronic polarization and decreases the HOMOCP?LUMOMVK gap,thereby improving the electron transfer capability between molecular orbitals,strengthening the interactions between bonding atoms in the transition state,and facilitating interfragment charge transfer.These effects stabilize the transition state and lower the activation barrier.Furthermore,electronic structure descriptors,including electrostatic potential,electron density difference,orbital energy gaps,fragment charges,and dipole moment,are provided to rationalize and predict the influence of OEEF on Diels?Alder reactivity.