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Cavity frequency-dependent theory for vibrational polariton chemistry

Author

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  • Xinyang Li

    (University of Rochester)

  • Arkajit Mandal

    (University of Rochester)

  • Pengfei Huo

    (University of Rochester
    University of Rochester)

Abstract

Recent experiments demonstrate the control of chemical reactivities by coupling molecules inside an optical microcavity. In contrast, transition state theory predicts no change of the reaction barrier height during this process. Here, we present a theoretical explanation of the cavity modification of the ground state reactivity in the vibrational strong coupling (VSC) regime in polariton chemistry. Our theoretical results suggest that the VSC kinetics modification is originated from the non-Markovian dynamics of the cavity radiation mode that couples to the molecule, leading to the dynamical caging effect of the reaction coordinate and the suppression of reaction rate constant for a specific range of photon frequency close to the barrier frequency. We use a simple analytical non-Markovian rate theory to describe a single molecular system coupled to a cavity mode. We demonstrate the accuracy of the rate theory by performing direct numerical calculations of the transmission coefficients with the same model of the molecule-cavity hybrid system. Our simulations and analytical theory provide a plausible explanation of the photon frequency dependent modification of the chemical reactivities in the VSC polariton chemistry.

Suggested Citation

  • 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.
  • Handle: RePEc:nat:natcom:v:12:y:2021:i:1:d:10.1038_s41467-021-21610-9
    DOI: 10.1038/s41467-021-21610-9
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    Citations

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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.
    4. Connor K. Terry Weatherly & Justin Provazza & Emily A. Weiss & Roel Tempelaar, 2023. "Theory predicts UV/vis-to-IR photonic down conversion mediated by excited state vibrational polaritons," Nature Communications, Nature, vol. 14(1), pages 1-12, December.
    5. Tao E. Li & Abraham Nitzan & Joseph E. Subotnik, 2022. "Energy-efficient pathway for selectively exciting solute molecules to high vibrational states via solvent vibration-polariton pumping," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    6. Kaihong Sun & Raphael F. Ribeiro, 2024. "Theoretical formulation of chemical equilibrium under vibrational strong coupling," Nature Communications, Nature, vol. 15(1), pages 1-12, December.
    7. Sindhana Pannir-Sivajothi & Jorge A. Campos-Gonzalez-Angulo & Luis A. Martínez-Martínez & Shubham Sinha & Joel Yuen-Zhou, 2022. "Driving chemical reactions with polariton condensates," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    8. 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.

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