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Computational study on the catalytic control of endo/exo Diels-Alder reactions by cavity quantum vacuum fluctuations

Author

Listed:
  • Fabijan Pavošević

    (Flatiron Institute)

  • Robert L. Smith

    (Flatiron Institute
    Virginia Tech)

  • Angel Rubio

    (Flatiron Institute
    Max Planck Institute for the Structure and Dynamics of Matter and Center for Free-Electron Laser Science & Department of Physics
    Universidad del País Vasco (UPV/EHU))

Abstract

Achieving control over chemical reaction’s rate and stereoselectivity realizes one of the Holy Grails in chemistry that can revolutionize chemical and pharmaceutical industries. Strong light-matter interaction in optical or nanoplasmonic cavities might provide the knob to reach such control. In this work, we demonstrate the catalytic and selectivity control of an optical cavity for two selected Diels-Alder cycloaddition reactions using the quantum electrodynamics coupled cluster (QED-CC) method. Herein, we find that by changing the molecular orientation with respect to the polarization of the cavity mode the reactions can be significantly inhibited or selectively enhanced to produce major endo or exo products on demand. This work highlights the potential of utilizing quantum vacuum fluctuations of an optical cavity to modulate the rate of Diels-Alder cycloaddition reactions and to achieve stereoselectivity in a practical and non-intrusive way. We expect that the present findings will be applicable to a larger set of relevant reactions, including the click chemical reactions.

Suggested Citation

  • 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.
    • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-38474-w
    DOI: 10.1038/s41467-023-38474-w
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    References listed on IDEAS

    as
    1. 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.
    2. 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.
    3. 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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