在电场下探索激活能量和反应能量之间的线性能量关系
Supin Zhao1, Ke Gong1, Zhexuan Song1
1Key Laboratory of Cluster Science of Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China.
Journal of chemical theory and computation
|April 17, 2025
概括
电场可以催化化学反应. 这项研究揭示了EFs下的激活和反应能量变化之间的线性能量关系 (LER),适用于高达1V/nm.
科学领域:
- 计算化学的计算化学
- 物理化学 物理化学
- 化学动力学 化学动力学
背景情况:
- 电场 (EF) 介导化学是由于其催化潜力的增长领域.
- 了解EF如何影响反应动力学和热力学至关重要.
研究的目的:
- 在EF下调查激活能量和反应能量变化之间的关系.
- 开发EF影响反应障碍的预测模型.
主要方法:
- 使用密度函数理论 (DFT) 和MP2计算.
- 该研究分析了包括SN2和质子转移在内的各种反应.
- 考虑了中性和带电系统,以及内热和外热过程.
主要成果:
- 在EF下,在激活和反应能量的变化之间观察到一个线性能量关系 (LER),ΔΔE‡ = mΔΔErxn.
- 该系数"m"近似的二极极矩变化的比例 (Δμ‡/Δμrxn).
- 在EF强度高达≈1V/nm时,LER是有效的,高场的偏差归因于EF诱导的几何变化和分子极化性.
结论:
- 在EF下提出了反应障碍的预测模型: -Δμ‡F - 0.5Δα‡F2,简化为 -Δμ‡F在低EF强度下.
- 已建立的LER和障碍预测模型为EF介导化学中的应用提供了显著的潜力.
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