Title: Limitations in Fluorescence-Detected Entangled Two-Photon-Absorption Experiments: Exploring the Low- to High-Gain Squeezing Regimes

Abstract: We closely replicated and extended a recent experiment ("Spatial properties of entangled two-photon absorption," Phys. Rev. Lett. 129, 183601, 2022) that reportedly observed enhancement of two-photon absorption rates in molecular samples by using time-frequency-entangled photon pairs, and we found that in the low-flux regime, where such enhancement is theoretically predicted in-principle, the two-photon fluorescence signal is below detection threshold using current state-of-the-art methods. The results are important in the context of efforts to enable quantum-enhanced molecular spectroscopy and imaging at ultra-low optical flux. Using an optical parametric down-conversion photon-pair source that can be varied from the low-gain spontaneous regime to the high-gain squeezing regime, we observed two-photon-induced fluorescence in the high-gain regime but in the low-gain regime any fluorescence was below detection threshold. We supplemented the molecular fluorescence experiments with a study of nonlinear-optical sum-frequency generation, for which we are able to observe the low-to-high-gain crossover, thereby verifying our theoretical models and experimental techniques. The observed rates (or lack thereof) in both experiments are consistent with theoretical predictions and with our previous experiments, and indicate that time-frequency photon entanglement does not provide a practical means to enhance in-solution molecular two-photon fluorescence spectroscopy or imaging with current techniques.