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

Year: 2024

Authors: Dutta A., Tiainen V., Sokolovskii I., Duarte L., Markesevic N., Morozov D., Qureshi HA., Pikker S., Groenhof G., Toppari JJ.

Autors Affiliation: Univ Jyvaskyla, Nanosci Ctr, POB 35, Jyvaskyla 40014, Finland; Univ Jyvaskyla, Dept Phys, POB 35, Jyvaskyla 40014, Finland; Univ Jyvaskyla, Dept Chem, POB 35, Jyvaskyla 40014, Finland; Univ Tartu, Inst Phys, W Ostwaldi 1, EE-50411 Tartu, Estonia; Univ Turku, Dept Mech & Mat Engn, Turku 20014, Finland; Univ Helsinki, Dept Chem, POB 55, Helsinki 00014, Finland; CNR, CNR INO Ist Nazl Ott, Via Nello Carrara 1, I-50019 Sesto Fiorentino, Italy; LENS European Lab Nonlinear Spect, Via Nello Carrara 1, I-50019 Sesto Fiorentino, Italy.

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. The aim of polaritonic chemistry is to control photochemical reactions by placing molecules inside optical cavities. Here, the authors show that this is not directly possible due to thermal disorder, which is unavoidable in real experiments, and polaritons mostly channel molecular excitations.

Journal/Review: NATURE COMMUNICATIONS

Volume: 15 (1)      Pages from: 6600-1  to: 6600-10

More Information: We thank Satu Mustalahti, Ossi Hakamaa, Mikael Kautto, Oskar Celik, Ruth H. Tichauer, Pasi Myllyperkioe, Tatu Kumpulainen, Thomas Fuhrmann-Lieker, and Thomas Kusserow for their assistance at various stages of the project. 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 Jyvaeskylae), 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. DAS:All data, including raw and analyzed experimental spectra with analyzing scripts, transfer matrix and FDTD modeling data and scripts, simulations models, input files, trajectories and structures, analysis scripts and programs, including raw data, are available for download from IDA-Research Data Storage71. Source data are provided with this paper.
KeyWords: Photoactive Yellow Protein; Density-functional Theory; Molecular-dynamics; Quantum; Field; Hybridization; Polaritons; Excitons; Proton
DOI: 10.1038/s41467-024-50532-5

Citations: 2
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