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Thermal disorder prevents the suppression of ultra-fast photochemistry in the strong light-matter coupling regime

Author

Listed:
  • Arpan Dutta

    (University of Jyväskylä
    University of Turku)

  • Ville Tiainen

    (University of Jyväskylä)

  • Ilia Sokolovskii

    (University of Jyväskylä)

  • Luís Duarte

    (University of Jyväskylä
    University of Helsinki)

  • Nemanja Markešević

    (University of Jyväskylä
    CNR-INO Istituto Nazionale di Ottica del Consiglio Nazionale delle Ricerche and LENS European Laboratory for Nonlinear Spectroscopy)

  • Dmitry Morozov

    (University of Jyväskylä)

  • Hassan A. Qureshi

    (University of Jyväskylä
    University of Turku)

  • Siim Pikker

    (University of Jyväskylä
    University of Tartu)

  • Gerrit Groenhof

    (University of Jyväskylä)

  • J. Jussi Toppari

    (University of Jyväskylä)

Abstract

Strong coupling between molecules and confined light modes of optical cavities to form polaritons can alter photochemistry, but the origin of this effect remains largely unknown. While theoretical models suggest a suppression of photochemistry due to the formation of new polaritonic potential energy surfaces, many of these models do not account for the energetic disorder among the molecules, which is unavoidable at ambient conditions. Here, we combine simulations and experiments to show that for an ultra-fast photochemical reaction such thermal disorder prevents the modification of the potential energy surface and that suppression is due to radiative decay of the lossy cavity modes. We also show that the excitation spectrum under strong coupling is a product of the excitation spectrum of the bare molecules and the absorption spectrum of the molecule-cavity system, suggesting that polaritons can act as gateways for channeling an excitation into a molecule, which then reacts normally. Our results therefore imply that strong coupling provides a means to tune the action spectrum of a molecule, rather than to change the reaction.

Suggested Citation

  • Arpan Dutta & Ville Tiainen & Ilia Sokolovskii & Luís Duarte & Nemanja Markešević & Dmitry Morozov & Hassan A. Qureshi & Siim Pikker & Gerrit Groenhof & J. Jussi Toppari, 2024. "Thermal disorder prevents the suppression of ultra-fast photochemistry in the strong light-matter coupling regime," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-50532-5
    DOI: 10.1038/s41467-024-50532-5
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    References listed on IDEAS

    as
    1. Javier Galego & Francisco J. Garcia-Vidal & Johannes Feist, 2016. "Suppressing photochemical reactions with quantized light fields," Nature Communications, Nature, vol. 7(1), pages 1-6, December.
    2. D. G. Lidzey & D. D. C. Bradley & M. S. Skolnick & T. Virgili & S. Walker & D. M. Whittaker, 1998. "Strong exciton–photon coupling in an organic semiconductor microcavity," Nature, Nature, vol. 395(6697), pages 53-55, September.
    3. Yi Yu & Suman Mallick & Mao Wang & Karl Börjesson, 2021. "Barrier-free reverse-intersystem crossing in organic molecules by strong light-matter coupling," Nature Communications, Nature, vol. 12(1), pages 1-8, December.
    4. Kati Stranius & Manuel Hertzog & Karl Börjesson, 2018. "Selective manipulation of electronically excited states through strong light–matter interactions," Nature Communications, Nature, vol. 9(1), pages 1-7, December.
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