A Roadmap Toward the Theory of Vibrational Polariton Chemistry
A Roadmap Toward the Theory of Vibrational Polariton Chemistry
复制标题
振动极化子化学理论路线图
DOI：
10.1021/acsphotonics.1c01028
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发表时间：
2021
期刊：
影响因子：
7
通讯作者：
Yelin, Susanne F.
中科院分区：
文献类型：
--
作者：
Wang, Derek S.;Yelin, Susanne F.
振动极化化学领域是在2016年建立的，当时在一个谐振调谐的红外腔内改变了室温下的化学反应速率，而无需外部驱动系统。尽管世界各地的科学家都在努力了解反应速率变化的原因，但没有令人信服的理论解释。在这个视角中，首先，我们简要回顾了这个开创性的实验，以及此后暗示反应物浓度、空腔频率和对称性作用的相关实验。然后，我们分析了主要理论的相关性，如量子电动力学修正的跃迁速率理论，光子溶剂笼效应，暗态耗散的影响，通过分子内振动能量重新分配增强键，以及共同增强局部分子性质。最后，我们通过提出实验来检验理论和为理论工作者提供新的途径，构建了振动极化化学理论的发展路线图。我们认为，理解强耦合机制开始的重要性，设计实验来捕捉反应途径的变化，探索空腔的完全色散，以及进一步发展空腔修饰分子内振动能量再分配和共同增强局部分子性质的理论是至关重要的下一步。我们希望这一展望能成为指导振动极化化学领域研究的宝贵资源。
The field of vibrational polariton chemistry was firmly established in 2016 when a chemical reaction rate at room temperature was modified within a resonantly tuned infrared cavity without externally driving the system. Despite intense efforts by scientists around the world to understand why the reaction rate changes, no convincing theoretical explanation exists. In this Perspective, first, we briefly review this seminal experiment, as well as relevant experiments that have since followed that have hinted at the roles of reactant concentration, cavity frequency, and symmetry. Then, we analyze the relevance of leading theories, such as quantum electrodynamics-modified transition rate theories, the photonic solvent cage effect, the impact of dissipation from dark states, bond strengthening via intramolecular vibrational energy redistribution, and collectively enhanced local molecular properties. Finally, we construct a roadmap toward the theory of vibrational polariton chemistry by suggesting experiments to test theories and new paths for theorists. We believe that understanding the importance of the onset of the strong coupling regime, designing experiments to capture changes in reaction pathways, exploring the full dispersion of cavities, and further developing the theories of cavity-modified intramolecular vibrational energy redistribution and collectively enhanced local molecular properties are crucial next steps. We hope this Perspective will be a valuable resource for guiding research in the field of vibrational polariton chemistry.
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