Schwartz Tal, Hutchison James A
School of Chemistry, Raymond and Beverly Sackler Faculty of Exact Sciences and Center for Light-Matter Interaction, Tel Aviv University, Tel Aviv, 6997801, Israel.
School of Chemistry and Australian Research Council Centre of Excellence in Exciton Science, The University of Melbourne, Masson Rd, Parkville, VIC, 3052, Australia.
Adv Mater. 2025 Jun;37(24):e2404602. doi: 10.1002/adma.202404602. Epub 2025 Apr 13.
Recently, an article by Barnes and co-workers reported an in-depth experimental re-evaluation of the earlier work on photoisomerization reactions inside optical cavities under conditions of strong light-matter coupling. That earlier work, which constituted the first demonstration of 'polaritonic chemistry', associated cavity-induced modifications of photoisomerization rates with the emergence of strong light-matter coupling (and the formation of polaritonic states). Barnes and co-workers instead found that cavity-induced changes in light absorption can account for changes in the photochemical reaction rates. While Barnes and co-workers correctly highlight the importance of controlling irradiation conditions from sample to sample where optical cavities are involved, this comment aims to emphasize the great length the original study went to ensure exactly this. The original experimental methods are summarized to point out the significant differences between them and those conducted by Barnes and co-workers. Furthermore, the importance of monochromatic photoexcitation at an isosbestic point rather than using broadband (UV through to IR) irradiation, as well as the careful control for photon flux reaching the molecular layer in all samples, as per the original work, is discussed. Further examination of important issues facing this new and developing domain of Physical Chemistry, is anticipated.
最近，巴恩斯及其同事的一篇文章报道了对早期关于强光-物质耦合条件下光学腔内光异构化反应工作的深入实验重新评估。早期的这项工作构成了“极化激元化学”的首次证明，将光异构化速率的腔诱导修饰与强光-物质耦合的出现（以及极化激元态的形成）联系起来。相反，巴恩斯及其同事发现，光吸收的腔诱导变化可以解释光化学反应速率的变化。虽然巴恩斯及其同事正确地强调了在涉及光学腔的情况下控制不同样品辐照条件的重要性，但本评论旨在强调原始研究为确保这一点所做的巨大努力。总结了原始实验方法，以指出它们与巴恩斯及其同事所进行的实验方法之间的显著差异。此外，还讨论了在等吸收点进行单色光激发而不是使用宽带（紫外到红外）辐照的重要性，以及按照原始工作对所有样品中到达分子层的光子通量进行仔细控制的重要性。预计将对物理化学这一新兴领域面临的重要问题进行进一步研究。
