Role of time-frequency correlations in two-photon–two-atom resonance energy transfer

Excitation energy transfer is a photophysical process upon which many chemical and biological phenomena are built. From natural small systems to synthetic multichromophoric macromolecules, energy transfer deals with the process of migration of electronic excitation energy from an excited donor to an acceptor. Although this phenomenon has been extensively studied in the past, the rapid evolution of quantum-enabled technologies has led to the question of whether nonclassical sources of light, such as entangled photon pairs, may provide us with better control (or enhancement) of energy transfer at the nanoscale. In this work we provide a comprehensive study of the joint excitation of two noninteracting two-level atoms by time-frequency-correlated photon pairs (whose central frequencies are not resonant with the individual particles) generated by means of spontaneous parametric down-conversion (SPDC). We demonstrate that while strong frequency anticorrelation between photons guarantees a large two-photon excitation (TPE) probability, photons bearing a sine cardinal spectral shape exhibit an approximately 3.8 times larger TPE signal than photons with a Gaussian spectrum. More importantly, we find that suppression of time-ordered excitation pathways does not substantially modify the TPE probability for two-photon states with a Gaussian spectral shape, whereas photons with a sine cardinal spectrum exhibit the strongest TPE signals when two-photon excitation pathways are not suppressed. Our results not only help elucidate the role of time-frequency correlations in resonance energy transfer with SPDC photons, but also provide valuable information regarding the optimal source to be used in the experimental implementation of said process.