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Shining light on the microscopic resonant mechanism responsible for cavity-mediated chemical reactivity

Author

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  • Christian Schäfer

    (Max Planck Institute for the Structure and Dynamics of Matter and Center for Free-Electron Laser Science & Department of Physics
    The Hamburg Center for Ultrafast Imaging
    Chalmers University of Technology
    Chalmers University of Technology)

  • Johannes Flick

    (Flatiron Institute
    Harvard University
    City College of New York
    City University of New York)

  • Enrico Ronca

    (Istituto per i Processi Chimico Fisici del CNR (IPCF-CNR))

  • Prineha Narang

    (Harvard University
    University of California, Los Angeles)

  • Angel Rubio

    (Max Planck Institute for the Structure and Dynamics of Matter and Center for Free-Electron Laser Science & Department of Physics
    The Hamburg Center for Ultrafast Imaging
    Flatiron Institute)

Abstract

Strong light–matter interaction in cavity environments is emerging as a promising approach to control chemical reactions in a non-intrusive and efficient manner. The underlying mechanism that distinguishes between steering, accelerating, or decelerating a chemical reaction has, however, remained unclear, hampering progress in this frontier area of research. We leverage quantum-electrodynamical density-functional theory to unveil the microscopic mechanism behind the experimentally observed reduced reaction rate under cavity induced resonant vibrational strong light-matter coupling. We observe multiple resonances and obtain the thus far theoretically elusive but experimentally critical resonant feature for a single strongly coupled molecule undergoing the reaction. While we describe only a single mode and do not explicitly account for collective coupling or intermolecular interactions, the qualitative agreement with experimental measurements suggests that our conclusions can be largely abstracted towards the experimental realization. Specifically, we find that the cavity mode acts as mediator between different vibrational modes. In effect, vibrational energy localized in single bonds that are critical for the reaction is redistributed differently which ultimately inhibits the reaction.

Suggested Citation

  • Christian Schäfer & Johannes Flick & Enrico Ronca & Prineha Narang & Angel Rubio, 2022. "Shining light on the microscopic resonant mechanism responsible for cavity-mediated chemical reactivity," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
  • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-35363-6
    DOI: 10.1038/s41467-022-35363-6
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    References listed on IDEAS

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    1. Oluwafemi S. Ojambati & Rohit Chikkaraddy & William D. Deacon & Matthew Horton & Dean Kos & Vladimir A. Turek & Ulrich F. Keyser & Jeremy J. Baumberg, 2019. "Quantum electrodynamics at room temperature coupling a single vibrating molecule with a plasmonic nanocavity," Nature Communications, Nature, vol. 10(1), pages 1-7, December.
    2. 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.
    3. Jorge A. Campos-Gonzalez-Angulo & Raphael F. Ribeiro & Joel Yuen-Zhou, 2019. "Resonant catalysis of thermally activated chemical reactions with vibrational polaritons," Nature Communications, Nature, vol. 10(1), pages 1-8, December.
    4. Xinyang Li & Arkajit Mandal & Pengfei Huo, 2021. "Cavity frequency-dependent theory for vibrational polariton chemistry," Nature Communications, Nature, vol. 12(1), pages 1-9, December.
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    Cited by:

    1. Lachlan P. Lindoy & Arkajit Mandal & David R. Reichman, 2023. "Quantum dynamical effects of vibrational strong coupling in chemical reactivity," Nature Communications, Nature, vol. 14(1), pages 1-14, December.
    2. Fabijan Pavošević & Robert L. Smith & Angel Rubio, 2023. "Computational study on the catalytic control of endo/exo Diels-Alder reactions by cavity quantum vacuum fluctuations," Nature Communications, Nature, vol. 14(1), pages 1-8, December.
    3. Qi Yu & Joel M. Bowman, 2023. "Manipulating hydrogen bond dissociation rates and mechanisms in water dimer through vibrational strong coupling," Nature Communications, Nature, vol. 14(1), pages 1-12, December.

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