Isolating Polaritonic 2D-IR Transmission Spectra

Abstract: Strong coupling between vibrational transitions in molecules within a resonant optical microcavity leads to the formation of collective, delocalized vibrational polaritons. There are many potential applications of "polaritonic chemistry," ranging from modified chemical reactivity to quantum in-formation processing. One challenge in obtaining the polaritonic response is to remove a background contribution due to the uncoupled molecules that generate an ordinary 2D-IR spectrum whose amplitude is filtered by the polariton transmission spectrum. We show that most features in 2D-IR spectra of vibrational polaritons can be explained by a linear superposition of this background signal and the true polariton response. Through a straightforward correction procedure, where the filtered bare molecule 2D-IR spectrum is subtracted from the measured cavity response, we recover the polaritonic spectrum.