Mandal Arkajit, Taylor Michael A D, Weight Braden M, Koessler Eric R, Li Xinyang, Huo Pengfei
Department of Chemistry, University of Rochester, 120 Trustee Road, Rochester, New York 14627, United States.
Department of Chemistry, Columbia University, New York, New York 10027, United States.
Chem Rev. 2023 Aug 23;123(16):9786-9879. doi: 10.1021/acs.chemrev.2c00855. Epub 2023 Aug 8.
When molecules are coupled to an optical cavity, new light-matter hybrid states, so-called polaritons, are formed due to quantum light-matter interactions. With the experimental demonstrations of modifying chemical reactivities by forming polaritons under strong light-matter interactions, theorists have been encouraged to develop new methods to simulate these systems and discover new strategies to tune and control reactions. This review summarizes some of these exciting theoretical advances in polariton chemistry, in methods ranging from the fundamental framework to computational techniques and applications spanning from photochemistry to vibrational strong coupling. Even though the theory of quantum light-matter interactions goes back to the midtwentieth century, the gaps in the knowledge of molecular quantum electrodynamics (QED) have only recently been filled. We review recent advances made in resolving gauge ambiguities, the correct form of different QED Hamiltonians under different gauges, and their connections to various quantum optics models. Then, we review recently developed ab initio QED approaches which can accurately describe polariton states in a realistic molecule-cavity hybrid system. We then discuss applications using these method advancements. We review advancements in polariton photochemistry where the cavity is made resonant to electronic transitions to control molecular nonadiabatic excited state dynamics and enable new photochemical reactivities. When the cavity resonance is tuned to the molecular vibrations instead, ground-state chemical reaction modifications have been demonstrated experimentally, though its mechanistic principle remains unclear. We present some recent theoretical progress in resolving this mystery. Finally, we review the recent advances in understanding the collective coupling regime between light and matter, where many molecules can collectively couple to a single cavity mode or many cavity modes. We also lay out the current challenges in theory to explain the observed experimental results. We hope that this review will serve as a useful document for anyone who wants to become familiar with the context of polariton chemistry and molecular cavity QED and thus significantly benefit the entire community.
当分子与光学腔耦合时，由于量子光与物质的相互作用，会形成新的光与物质的混合态，即所谓的极化激元。随着在强光与物质相互作用下通过形成极化激元来改变化学反应活性的实验证明，理论学家们受到鼓舞，去开发新方法来模拟这些系统，并发现调整和控制反应的新策略。本综述总结了极化激元化学中一些令人兴奋的理论进展，涵盖从基本框架到计算技术的方法，以及从光化学到振动强耦合的应用。尽管量子光与物质相互作用的理论可以追溯到20世纪中叶，但分子量子电动力学（QED）知识的空白直到最近才被填补。我们回顾了在解决规范模糊性、不同规范下不同QED哈密顿量的正确形式及其与各种量子光学模型的联系方面取得的最新进展。然后，我们回顾了最近开发的从头算QED方法，这些方法可以准确描述实际分子 - 腔混合系统中的极化激元态。接着，我们讨论使用这些方法进展的应用。我们回顾了极化激元光化学的进展，其中使腔与电子跃迁共振以控制分子非绝热激发态动力学并实现新的光化学反应活性。当腔共振调谐到分子振动时，尽管其机理原理仍不清楚，但已通过实验证明了基态化学反应的改变。我们展示了在解开这个谜团方面的一些最新理论进展。最后，我们回顾了在理解光与物质的集体耦合机制方面的最新进展，其中许多分子可以集体耦合到单个腔模或多个腔模。我们还阐述了目前理论上解释观察到的实验结果所面临的挑战。我们希望这篇综述能为任何想熟悉极化激元化学和分子腔QED背景的人提供一份有用的文档，从而使整个社区受益匪浅。
