In this study, we overview resonance energy transfer between molecules in the presence of plasmonic structures and derive an explicit Förster-type expression for the rate of plasmon-coupled resonance energy transfer (PC-RET). The proposed theory is general for energy transfer in the presence of materials with any space-dependent, frequency-dependent, or complex dielectric functions. Furthermore, the theory allows us to develop the concept of a generalized spectral overlap (GSO) J̃ (the integral of the molecular absorption coefficient, normalized emission spectrum, and the plasmon coupling factor) for understanding the wavelength dependence of PC-RET and to estimate the rate of PC-RET W. Indeed, W = (8.785 × 10 mol) ϕτJ̃, where ϕ is donor fluorescence quantum yield and τ is the emission lifetime. Simulations of the GSO for PC-RET show that the most important spectral region for PC-RET is not necessarily near the maximum overlap of donor emission and acceptor absorption. Instead a significant plasmonic contribution can involve a different spectral region from the extinction maximum of the plasmonic structure. This study opens a promising direction for exploring exciton transport in plasmonic nanostructures, with possible applications in spectroscopy, photonics, biosensing, and energy devices.

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This paper presents a new real-time electrodynamics approach for determining the rate of resonance energy transfer (RET) between two molecules in the presence of plasmonic or other nanostructures (inhomogeneous absorbing and dispersive media). In this approach to plasmon-coupled resonance energy transfer (PC-RET), we develop a classical electrodynamics expression for the energy transfer matrix element which is evaluated using the finite-difference time-domain (FDTD) method to solve Maxwell's equations for the electric field generated by the molecular donor and evaluated at the position of the molecular acceptor. We demonstrate that this approach yields RET rates in homogeneous media that are in precise agreement with analytical theory based on quantum electrodynamics (QED). In the presence of gold nanoparticles, our theory shows that the long-range decay of the RET rates can be significantly modified by plasmon excitation, with rates increased by as much as a factor of 10 leading to energy transfer rates over hundreds of nm that are comparable to that over tens of nm in the absence of the nanoparticles. These promising results suggest important future applications of the PC-RET in areas involving light harvesting or sensing, where energy transfer processes involving inhomogeneous absorbing and dispersive media are commonplace.

One of the strengths of molecular electronics is the synthetic ability of tuning the electric properties by the derivatization and reshaping of the functional moieties. However, after the quantitative measurements of single-molecule resistance became available, it was soon apparent that the assumption of negligible influence of the headgroup-electrode contact on the molecular resistance was oversimplified. Due to the measurement scheme of the metal--molecule-metal configuration, the contact resistance is always involved in the reported values. Consequently the electrical behavior of the tailored molecular moiety can only be conceptually inferred by the tunneling decay constant (βn in Rmeasured = R(n=0)e(βnN), where N is the number of repeated units), available only for compounds with a homologous series. This limitation hampers the exploration of novel structures for molecular devices. Based on the Landauer formula, we propose that the single-molecule resistance of the molecular backbones can be extracted. This simplified evaluation scheme is cross-examined by electrode materials of Au, Pd, and Pt and by anchoring groups of thiol (-SH), nitrile (-CN), and isothiocyanate (-NCS). The resistance values of molecular backbones for polymethylenes (n = 4, 6, 8, and 10) and phenyl (-C6H4-) moieties are found independent of the anchoring groups and electrode materials. The finding justifies the proposed approach that the resistance of functional moieties can be quantitatively evaluated from the measured values even for compounds without repeated units.

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 chargeantisymmetric 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.