Wang Siwei, Scholes Gregory D, Hsu Liang-Yan
Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan.
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
J Phys Chem Lett. 2020 Aug 6;11(15):5948-5955. doi: 10.1021/acs.jpclett.0c01680. Epub 2020 Jul 13.
We investigate the coherent-to-incoherent transition of molecular fluorescence of a chromophore above a silver surface (including bulk and thin-film systems) and explore the distance dependence of fluorescence rate enhancement. In the framework of macroscopic quantum electrodynamics, we generalize our previous theory to include multiple vibrational modes. The present theory can accurately describe quantum dynamics from the coherent limit to the incoherent limit. Moreover, we introduce a new concept to quantify the degree of quantum coherence and demonstrate that the coherent-to-incoherent transition can be controlled by the dielectric environment and the molecule-silver distance. In addition, our theory indicates that strong molecule-photon (polariton) coupling can be achieved by virtue of small Huang-Rhys factors, large transition dipole moments, and appropriate dielectric material design. The present study provides a new direction for engineering light-matter interactions in polaritonic chemistry.
我们研究了发色团在银表面（包括体材料和薄膜系统）上方分子荧光的相干到非相干转变，并探讨了荧光速率增强的距离依赖性。在宏观量子电动力学框架下，我们将先前的理论进行推广，纳入多个振动模式。当前理论能够准确描述从相干极限到非相干极限的量子动力学。此外，我们引入一个新概念来量化量子相干程度，并证明相干到非相干的转变可由介电环境和分子与银的距离控制。另外，我们的理论表明，借助小的黄昆 - 里斯因子、大的跃迁偶极矩以及合适的介电材料设计，可以实现强的分子 - 光子（极化激元）耦合。本研究为极化子化学中光与物质相互作用的工程设计提供了新方向。
