Shining Light on the Microscopic Resonant Mechanism Responsible for Cavity-Mediated Chemical Reactivity

(submitted), (2021)

Shining Light on the Microscopic Resonant Mechanism Responsible for Cavity-Mediated Chemical Reactivity

Christian Schäfer, Johannes Flick, Enrico Ronca, Prineha Narang, Angel Rubio

Strong light-matter interaction in cavity environments has emerged as a promising and general approach to control chemical reactions in a non-intrusive manner. The underlying mechanism that distinguishes between steering, accelerating, or decelerating a chemical reaction has, however, remained thus far largely unclear, hampering progress in this frontier area of research. In this work, we leverage a combination of first-principles techniques, foremost quantum-electrodynamical density functional theory, applied to the recent experimental realization by Thomas et al. [1] to unveil the microscopic mechanism behind the experimentally observed reduced reaction-rate under resonant vibrational strong light-matter coupling. We find that the cavity mode functions as a mediator between different vibrational eigenmodes, transferring vibrational excitation and anharmonicity, correlating vibrations, and ultimately strengthening the chemical bond of interest. Importantly, the resonant feature observed in experiment, theoretically elusive so far, naturally arises in our investigations. Our theoretical predictions in polaritonic chemistry shine new light on cavity induced mechanisms, providing a crucial control strategy in state-of-the-art photocatalysis and energy conversion, pointing the way towards generalized quantum optical control of chemical systems.

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We thank Anoop Thomas, Thomas Ebbesen, Michael Ruggenthaler, and Goran Johansson for insightful discussions. This work was supported by the European Research Council (ERC-2015-AdG694097), the Cluster of Excellence 'Advanced Imaging of Matter' (AIM), Grupos Consolidados (IT1249-19), partially by the Federal Ministry of Education and Research Grant RouTe-13N14839, the SFB925 "Light induced dynamics and control of correlated quantum systems", the Swedish Research Council (VR) through Grant No. 2016-06059, the Department of Energy, Photonics at Thermodynamic Limits Energy Frontier Research Center, under Grant No. DESC0019140. The Flatiron Institute is a division of the Simons Foundation. P.N. gratefully acknowledges a Moore Inventor Fellowship through Grant GBMF8048 from the Gordon and Betty Moore Foundation and support from the CIFAR BSE Program's `Catalyst' grant.

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