Fundamental figures of merit for engineering Forster resonance energy transfer

Abstract

Over the past 15 years there has been an ongoing debate regarding the influence of the photonic environment on Forster resonance energy transfer (FRET). Disparate results corresponding to enhancement, suppression and null effect of the photonic environment have led to a lack of consensus between the traditional theory of FRET and experiments. Here we show that the quantum electrodynamic theory of FRET near an engineered nanophotonic environment is exactly equivalent to an effective near-field model describing electrostatic dipole-dipole interactions. This leads to an intuitive and rigorously exact description of FRET bridging the gap between experimental observations and theoretical interpretations. We show that the widely used concept of the Purcell factor is only important for understanding spontaneous emission and is an incorrect figure of merit for analyzing FRET. To this end, we analyze the figures of merit which characterize FRET in a photonic environment: (1) the FRET rate enhancement factor ($F_{ET}$), (2) the FRET efficiency enhancement factor ($F_{eff}$) and (3) the two-point spectral density ($S_{EE}$) governing FRET analogous to the local density of states that controls spontaneous emission. Counterintuitive to existing knowledge, we show that suppression of the Purcell factor is in fact necessary for enhancing the efficiency of the FRET process. We place fundamental bounds on the FRET figures of merit arising from material absorption in the photonic environment as well as key properties of emitters including intrinsic quantum efficiencies and orientational dependence. Finally, we use our approach to conclusively explain recent experiments and predict regimes where the FRET rate is expected to be enhanced, suppressed or remain the same. Our work paves for a complete theory of FRET with predictive power for designing the ideal photonic environment to control FRET.