2022/11/29 by Connor K. Terry Weatherly, Justin Provazza, Weatherly, Connor K. Terry +5
Chemistry · Materials Science · Physics and Astronomy · #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Photochemistry and Electron Transfer Studies #Porphyrin and Phthalocyanine Chemistry #Strong Light-Matter Interactions
paper · pdf · doi:10.48550/arxiv.2211.16613
openalex publication_date 2022/11/29 · openalex created_date 2022/12/12 · openalex updated_date 2026/07/28
This work proposes a new photophysical phenomenon whereby UV/vis excitation of a molecule involving a Franck-Condon (FC) active vibration yields infrared (IR) emission by strong coupling to an optical cavity. The resulting UV/vis-to-IR photonic down conversion process is mediated by vibrational polaritons in the electronic excited state potential. It is shown that the formation of such excited state vibrational polaritons (ESVP) via UV/vis excitation only occurs with molecules having vibrational modes with both a non-zero FC activity and IR activity in the excited state. Density functional theory calculations are shown to effectively identify a candidate molecule, 1-Pyreneacetic acid (PAA), with this property and the dynamics of ESVP are modeled using the truncated Wigner approximation. Overall, this work presents a new avenue of polariton chemistry where excited state dynamics, driven by photoexcitation, are influenced by the formation of vibrational polaritons. Along with this, the photonic down conversion is potentially useful in both the sensing of excited state vibrations and in quantum transduction schemes.