A1 Refereed original research article in a scientific journal
Thermal disorder prevents the suppression of ultra-fast photochemistry in the strong light-matter coupling regime
Authors: Dutta, Arpan; Tiainen, Ville; Sokolovskii, Ilia; Duarte, Luís; Markešević, Nemanja; Morozov, Dmitry; Qureshi, Hassan A.; Pikker, Siim; Groenhof, Gerrit; Toppari, J. Jussi
Publisher: Springer Nature
Publication year: 2024
Journal: Nature Communications
Journal name in source: Nature communications
Journal acronym: Nat Commun
Article number: 6600
Volume: 15
Issue: 1
eISSN: 2041-1723
DOI: https://doi.org/10.1038/s41467-024-50532-5
Web address : https://www.nature.com/articles/s41467-024-50532-5
Self-archived copy’s web address: https://research.utu.fi/converis/portal/detail/Publication/457448705
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.
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Funding information in the publication:
This work was supported by the Academy of Finland via Research projects (Grants Nos. 323996 and 332743 to G.G., Nos. 323995, 289947 and 350797 to J.J.T.) and University profiling funding (Profi4 to University of Jyväskylä), with contributions from the Finnish Cultural Foundation (Grant No. 00231164 to J.J.T. and G.G.) and the Estonian Research Council (Grant No. PSG406 to S.P.). We also thank the Center for Scientific Computing (CSC-IT Center for Science) for generous computational resources for G.G.
