中央研究院 原子與分子科學研究所

In this study, we develop a theory of multichromophoric excitation energy transfer (MC-EET) in the framework of macroscopic quantum electrodynamics. The theory we present is general for studying the interplay between energy transfer and fluorescence in the presence of arbitrary inhomogeneous, dispersive, and absorbing media. The dynamical equations of MC-EET, including energy-transfer kernels and fluorescence kernels, allow us to describe the combined effects of molecular vibrations and photonic environments on excitation energy transfer. To demonstrate the universality of the MC-EET theory, we show that under specific conditions, the MC-EET theory can be converted to three representative theories. First, under the Markov approximation, we derive an explicit Förster-type expression for plasmon-coupled resonance energy transfer [Hsu et al., J. Phys. Chem. Lett. 8, 2357 (2017)] from the MC-EET theory. In addition, the MC-EET theory also provides a parameter-free formula to estimate transition dipole–dipole interactions mediated by photonic environments. Second, we generalize the theory of multichromophoric Förster resonance energy transfer [Jang et al., Phys. Rev. Lett. 92, 218301 (2004)] to include the effects of retardation and dielectric environments. Third, for molecules weakly coupled with photonic modes, the MC-EET theory recovers the previous main result in Chance–Prock–Silbey classical fluorescence theory [Chance et al., J. Chem. Phys. 60, 2744 (1974)]. This study opens a promising direction for exploring light–matter interactions in multichromophoric systems with possible applications in the exciton migration in metal–organic framework materials and organic photovoltaic devices.

Richard Feynman stated that “The theory behind chemistry is quantum electrodynamics”. However, harnessing quantum-electrodynamic (QED) effects to modify chemical reactions is a grand challenge and currently has only been reported in experiments using cavities due to the limitation of strong light–matter coupling. In this article, we demonstrate that QED effects can significantly enhance the rate of electron transfer (ET) by several orders of magnitude in the absence of cavities, which is implicitly supported by experimental reports. To understand how cavity-free QED effects are involved in ET reactions, we incorporate the effect of infinite one-photon states into Marcus theory, derive an explicit expression for the rate of radiative ET, and develop the concept of “electron transfer overlap”. Moreover, QED effects may lead to a barrier-free ET reaction whose rate is dependent on the energy-gap power law. This study thus provides new insights into fundamental chemical principles, with promising prospects for QED-based chemical reactions.

Our previous study [S. Wang et al., J. Chem. Phys. 153, 184102 (2020)] has shown that in a complex dielectric environment, molecular emission power spectra can be expressed as the product of the lineshape function and the electromagnetic environment factor (EEF). In this work, we focus on EEFs in a vacuum–NaCl–silver system and investigate molecular emission power spectra in the strong exciton–polariton coupling regime. A numerical method based on computational electrodynamics is presented to calculate the EEFs of single-molecule emitters in a dispersive and lossy dielectric environment with arbitrary shapes. The EEFs in the far-field region depend on the detector position, emission frequency, and molecular orientation. We quantitatively analyze the asymptotic behavior of the EFFs in the far-field region and qualitatively provide a physical picture. The concept of EEF should be transferable to other types of spectra in a complex dielectric environment. Finally, our study indicates that molecular emission power spectra cannot be simply interpreted by the lineshape function (quantum dynamics of a molecular emitter), and the effect of the EEFs (photon propagation in a dielectric environment) has to be carefully considered.

We study the emission power spectrum of a molecular emitter with multiple vibrational modes in the framework of macroscopic quantum electrodynamics. The theory we present is general for a molecular spontaneous emission spectrum in the presence of arbitrary inhomogeneous, dispersive, and absorbing media. Moreover, the theory shows that the molecular emission power spectra can be decomposed into the electromagnetic environment factor and lineshape function. In order to demonstrate the validity of the theory, we investigate the lineshape function in two limits. In the incoherent limit (single molecules in a vacuum), the lineshape function exactly corresponds to the Franck–Condon principle. In the coherent limit (single molecules strongly coupled with single polaritons or photons) together with the condition of high vibrational frequency, the lineshape function exhibits a Rabi splitting, the spacing of which is exactly the same as the magnitude of exciton–photon coupling estimated by our previous theory [S. Wang et al., J. Chem. Phys. 151, 014105 (2019)]. Finally, we explore the influence of exciton–photon and electron–phonon interactions on the lineshape function of a single molecule in a cavity. The theory shows that the vibronic structure of the lineshape function does not always disappear as the exciton–photon coupling increases, and it is related to the loss of a dielectric environment.

Large-scale inhomogeneous plasmonic metal chips have been demonstrated as a promisingplatform for biochemical sensing, but the origin of their strong fluorescence enhancementsand average gap dependence is a challenging issue due to the complexity of modelingtremendous molecules within inhomogeneous gaps. To address this issue, we bridgedmicroscopic mechanisms and macroscopic observations, developed a kinetic model, andexperimentally investigated the fluorescence enhancement factors of IR800-streptavidinimmobilized on metal nanoisland films (NIFs). Inspired by the kinetic model, we controlledthe distribution of IR800-streptavidin within the valleys of NIFs by regioselectivemodification and achieved the fluorescence intensity enhancement up to 488-fold. Thekinetic model allows us to qualitatively explain the mechanism of fluorescence intensityenhancements and quantitatively predict the trend of experimental enhancement factors,thereby determining the design principles of the plasmonic metal chips. Our studyprovides one key step further toward the sensing applications of large-scale plasmonicmetal chips.

We investigate the intrinsic characteristics of resonance energy transfer (RET) coupled with localized surface plasmon polaritons (LSPPs) from the perspective of macroscopic quantum electrodynamics. To quantify the effect of LSPPs, we propose a numerical scheme that allows us to accurately calculate the rate of RET between a donor–acceptor pair near a nanoparticle. Our study shows that LSPPs can be used to enhance the RET rate significantly and control its frequency dependence by modifying a core/shell structure, which indicates the possibility of RET rate optimization. Moreover, we systematically explore the angle (distance) dependence of the RET rate and analyze its origin. According to different frequency regimes, the angle dependence of RET is dominated by different mechanisms, such as LSPPs, surface plasmon polaritons (SPPs), and anti-resonance. For the proposed core/shell structure, the characteristic distance of RET coupled with LSPPs (approximately 0.05 emission wavelength) is shorter than that of RET coupled with SPPs (approximately 0.1 emission wavelength), which may provide promising applications in energy science.