Fassioli Francesca, Park Kyu Hyung, Bard Sarah E, Scholes Gregory D
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
SISSA - Scuola Internazionale Superiore di Studi Avanzati, Trieste 34136, Italy.
J Phys Chem Lett. 2021 Nov 25;12(46):11444-11459. doi: 10.1021/acs.jpclett.1c03183. Epub 2021 Nov 18.
Molecular polaritons are hybrid states of photonic and molecular character that form when molecules strongly interact with light. Strong coupling tunes energy levels and, importantly, can modify molecular properties (e.g., photoreaction rates), opening an avenue for novel polariton chemistry. In this Perspective, we focus on the collective aspects of strongly coupled molecular systems and how this pertains to the dynamical response of such systems, which, though of key importance for attaining modified function under polariton formation, is still not well-understood. We discuss how the ultrafast time and spectral resolution make pump-probe spectroscopy an ideal tool to reveal the energy-transfer pathways from polariton states to other molecular states of functional interest. Finally, we illustrate how analyzing the free (rather than electronic) energy structure in molecular polariton systems may provide new clues into how energy flows and thus how strong coupling may be exploited.
分子极化激元是光子特性与分子特性的混合态，当分子与光发生强烈相互作用时形成。强耦合会调整能级，重要的是，还能改变分子性质（如光反应速率），为新型极化激元化学开辟了一条途径。在这篇综述文章中，我们关注强耦合分子体系的集体特性，以及这与此类体系的动力学响应有何关联，尽管这对于在极化激元形成过程中实现功能改性至关重要，但目前仍未得到充分理解。我们讨论了超快时间和光谱分辨率如何使泵浦 - 探测光谱成为揭示从极化激元态到其他感兴趣功能分子态的能量转移途径的理想工具。最后，我们举例说明分析分子极化激元体系中的自由（而非电子）能量结构如何能为能量流动方式以及如何利用强耦合提供新线索。
