Experimental Upper Bounds for Resonance-Enhanced Entangled Two-Photon Absorption Cross Section of Indocyanine Green

Abstract: Resonant intermediate states have been proposed to increase the efficiency of entangled two-photon absorption (ETPA). Although resonance-enhanced ETPA (r-ETPA) has been demonstrated in atomic systems using bright squeezed vacuum, it has not been studied in organic molecules. We investigate for the first time r-ETPA in an organic molecular dye, indocyanine green (ICG), when excited by broadband entangled photons in near-IR. Similar to many reported virtual state mediated ETPA (v-ETPA) measurements, no r-ETPA signals are measured, with an experimental upper bound for the cross section placed at $6 \times 10^{-23}$ cm$^2$/molecule. In addition, the classical resonance-enhanced two-photon absorption (r-TPA) cross section of ICG at 800 nm is measured for the first time to be $20(\pm13)$ GM, suggesting that having a resonant intermediate state does not significantly enhance two-photon processes in ICG. The spectrotemporally resolved emission signatures of ICG excited by entangled photons are also presented to support this conclusion.