Garg Pallavi, Singh Jaibir, Gaur Ankit Kumar, Venkataramani Sugumar, Schäfer Christian, George Jino
Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER), Mohali, Punjab, India.
Condensed Matter and Materials Theory, Department of Physics, Chalmers University of Technology, Gothenburg, Sweden.
Commun Chem. 2025 Jul 1;8(1):192. doi: 10.1038/s42004-025-01588-x.
Strong light-matter interactions demonstrated considerable potential to control photochemical reactions. Here, we coupled a single cavity mode to the electronic S-S transition of azopyrrole E and Z-isomers. This allows us to observe the impact on the photoisomerization process "on-the-go", i.e., capturing a sharp transition in the kinetics when moving from strong to weak coupling. Pumping either at the upper polaritonic state or the uncoupled population shows an acceleration of the photoisomerization process (strong to weak), whereas the opposite is observed when exciting the lower polaritonic state. Excellent correlation between spectral overlap and rate suggests that changes in photochemistry are mediated by relaxation via the dark state manifold. Remaining in the ultra-strong coupling regime affects the reaction kinetics, but without sharp transitions. Our experimental and theoretical findings underline that dynamic transitions between coupling domains might pave the way to a better understanding of how strong coupling modifies photoisomerization reactions.
强光与物质相互作用显示出控制光化学反应的巨大潜力。在此，我们将单个腔模与偶氮吡咯E和Z异构体的电子S-S跃迁相耦合。这使我们能够“实时”观察对光异构化过程的影响，即在从强耦合转变为弱耦合时捕捉动力学中的急剧转变。在上部极化激元态或未耦合态进行泵浦时，光异构化过程（从强到弱）会加速，而激发下部极化激元态时则观察到相反的情况。光谱重叠与速率之间的良好相关性表明，光化学变化是通过经由暗态流形的弛豫介导的。保持在超强耦合 regime 会影响反应动力学，但不会出现急剧转变。我们的实验和理论结果强调，耦合域之间的动态转变可能为更好地理解强耦合如何改变光异构化反应铺平道路。 （注：原文中“regime”未准确翻译，可根据具体语境进一步优化，这里暂保留英文）
