Year: 2023
Type: article
Abstract: Most photochemistry occurs in the regime of weak light-matter coupling, in which a molecule absorbs a photon and then performs photochemistry from its excited state. In the strong coupling regime, enhanced light-matter interactions between an optical field and multiple molecules lead to collective hybrid light-matter states called polaritons. This strong coupling leads to fundamental changes in the nature of the excited states including multi-molecule delocalized excitations, modified potential energy surfaces, and dramatically altered energy levels relative to non-coupled molecules. The effect of strong light-matter coupling on covalent photochemistry has not been well explored. Photoswitches undergo reversible intramolecular photoreactions that can be readily monitored spectroscopically. In this work, we study the effect of strong light-matter coupling on the kinetics of photoswitching within optical cavities. Reproducing prior experiments, photoswitching of spiropyran/merocyanine photoswitches is decelerated in a cavity. Fulgide photoswitches, however, show the opposite effect, with strong coupling accelerating photoswitching. While modified merocyanine switching can be explained by changes in radiative decay rates or the amount of light in the cavity, modified fulgide switching kinetics suggest direct changes to excited-state reaction kinetics.
DOI: 10.1021/jacs.3c04254
Institutions: Northwestern University, University of California San Diego
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: green
Funders: National Science Foundation, U.S. Department of Energy, Northwestern University, Office of Science, Materials Research Science and Engineering Center, Harvard University, International Institute for Nanotechnology, Northwestern University, Materials Research Science and Engineering Center, Northwestern University, Division of Materials Research, Division of Graduate Education, Division of Electrical, Communications and Cyber Systems, Basic Energy Sciences, Energy Frontier Research Centers
Awards: G1169090945, G1276186940, G1329306526, G1541189025, CENTER FOR MOLECULAR QUANTUM TRANSDUCTION (CMQT), G2137585358, Graduate Research Fellowship Program (GRFP), G2714387552, CENTER FOR MOLECULAR QUANTUM TRANSDUCTION (CMQT), G336680401, G3454132534, G4207708471, G4285583887, G4289625387, G4433393426, MRSEC: Center for Multifunctional Materials, G4912152698, G5218300437, NNCI: Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource, G6101976803, G7304483037, G7461832402, G7570481651, G7727103928, G801469781, G8073314406, G810510296, G8230932042
OpenAlex ID: W4386245130