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

Christian Schäfer (), Johannes Flick (), Enrico Ronca (), Prineha Narang () and Angel Rubio ()
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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
Johannes Flick: Flatiron Institute
Enrico Ronca: Istituto per i Processi Chimico Fisici del CNR (IPCF-CNR)
Prineha Narang: Harvard University
Angel Rubio: Max Planck Institute for the Structure and Dynamics of Matter and Center for Free-Electron Laser Science & Department of Physics

Nature Communications, 2022, vol. 13, issue 1, 1-9

Abstract: 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.

Date: 2022
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DOI: 10.1038/s41467-022-35363-6

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