中央研究院 原子與分子科學研究所

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.
 

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 Incoherent Index 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.

We study a molecular emitter above a silver surface in the framework of macroscopic quantum electrodynamics and explore the population dynamics including non-Markovian effects. The theory we present is general for molecular fluorescence in the presence of dielectrics with any space-dependent, frequency-dependent, or complex dielectric functions. Furthermore, the proposed theory allows us to calculate the memory kernel of polaritons using computational electrodynamics packages. In the limit of a high vibration frequency, the different strengths of exciton-polariton couplings lead to distinct characteristics in the population dynamics, e.g., Franck-Condon-Rabi oscillation. (The frequency of Rabi oscillation is dependent on the Franck-Condon factor.) Additionally, in a specific condition, we derive a parameter-free formula that can be used to estimate the exciton-polariton coupling between a molecular emitter and a nanocavity, and the coupling estimated by our theory is in good agreement with the reported experimental results [Chikkaraddy et al., Nature 535, 127–130 (2016)].

We investigate resonance energy transfer (RET) between a donor–acceptor pair above a gold surface (including bulk and thin-film systems) and explore the distance/frequency dependence of RET enhancements using the theory we developed previously. The mechanism of RET above a gold surface can be attributed to the effects of mirror dipoles, surface plasmon polaritons (SPPs), and retardation. To clarify these effects on RET, we analyze the enhancements of RET by the mirror method, the decomposition of s- and p-polarization, and the SPP dispersion of charge-symmetric and charge-antisymmetric modes. We find a characteristic distance (approximately 1/10 of the wavelength) that can be used to classify the dominant effect on RET. Moreover, the characteristic distance can be shortened by narrowing the thickness of the thin-film systems, indicating that SPPs can enhance the rate of RET at a short range. The charge-symmetric and charge-antisymmetric modes of the thin films also allow us to engineer the maximum RET enhancement. We hope that our analysis inspires further investigation into the mechanism of RET coupled with SPPs and its applications.

In this study, we explore photoinduced electron transport through a molecule weakly coupled to two electrodes by combining first-principles quantum chemistry calculations with a Pauli master equation approach that accounts for many-electron states. In the incoherent limit, we demonstrate that energy-level alignment of triplet and charged states plays a crucial role, even when the rate of intersystem crossing is much smaller than the rate of fluorescence. Furthermore, the field intensity dependence and an upper bound to the photoinduced electric current can be analytically derived in our model. Under an optical field, the conductance spectra (charge stability diagrams) exhibit unusual Coulomb diamonds, which are associated with molecular excited states, and their widths can be expressed in terms of energies of the molecular electronic states. This study offers new directions for exploring optoelectronic response in nanoelectronics.