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Theoretical formulation of chemical equilibrium under vibrational strong coupling

Author

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  • Kaihong Sun

    (Emory University)

  • Raphael F. Ribeiro

    (Emory University)

Abstract

Experiments have suggested that strong interactions between molecular ensembles and infrared microcavities can be employed to control chemical equilibria. Nevertheless, the primary mechanism and key features of the effect remain largely unexplored. In this work, we develop a theory of chemical equilibrium in optical microcavities, which allows us to relate the equilibrium composition of a mixture in different electromagnetic environments. Our theory shows that in planar microcavities under strong coupling with polyatomic molecules, hybrid modes formed between all dipole-active vibrations and cavity resonances contribute to polariton-assisted chemical equilibrium shifts. To illustrate key aspects of our formalism, we explore a model SN2 reaction within a single-mode infrared resonator. Our findings reveal that chemical equilibria can be shifted towards either direction of a chemical reaction, depending on the oscillator strength and frequencies of reactant and product normal modes. Polariton-induced zero-point energy changes provide the dominant contributions, though the effects in idealized single-mode cavities tend to diminish quickly as the temperature and number of molecules increase. Our approach is valid in generic electromagnetic environments and paves the way for understanding and controlling chemical equilibria with microcavities.

Suggested Citation

  • 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.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-46442-1
    DOI: 10.1038/s41467-024-46442-1
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    References listed on IDEAS

    as
    1. 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.
    2. 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.
    3. 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.
    4. A. Shalabney & J. George & J. Hutchison & G. Pupillo & C. Genet & T. W. Ebbesen, 2015. "Coherent coupling of molecular resonators with a microcavity mode," Nature Communications, Nature, vol. 6(1), pages 1-6, May.
    5. Rohit Chikkaraddy & Bart de Nijs & Felix Benz & Steven J. Barrow & Oren A. Scherman & Edina Rosta & Angela Demetriadou & Peter Fox & Ortwin Hess & Jeremy J. Baumberg, 2016. "Single-molecule strong coupling at room temperature in plasmonic nanocavities," Nature, Nature, vol. 535(7610), pages 127-130, July.
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