Effect of Many Modes on Self-Polarization and Photochemical Suppression in Cavities

Journal of Chemical Physics 153, 10, 104103 (2020)

Effect of Many Modes on Self-Polarization and Photochemical Suppression in Cavities

Norah M. Hoffmann, Lionel Lacombe, Angel Rubio, Neepa T. Maitra

The standard description of cavity-modified molecular reactions typically involves a single (resonant)mode, while in reality the quantum cavity supports a range of photon modes. Here we demonstrate that as more photon modes are included, physico-chemical phenomena can dramatically change, as illustrated by the cavity-induced suppression of the important and ubiquitous process of proton-coupled electron-transfer. Using a multi-trajectory Ehrenfest treatment for the photonmodes,we find that self-polarization effects become essential, and we introduce the concept of selfpolarization-modified Born-Oppenheimer surfaces as a new construct to analyze dynamics. As the number of cavity photon modes increases, the interplay between photon emission and absorption inside the increasingly wide bands of these surfaces, together with their deviations from the cavityfree Born-Oppenheimer surfaces, leads to enhanced suppression. The present findings are general and will have implications for the description and control of cavity-driven physical processes of molecules, nanostructures and solids embedded in cavities.

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We would like to thank Johannes Feist for insightful discussions. Financial support from the US National Science Foundation CHE-1940333 (NM) and the Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences under Award de-sc0020044 (LL) are gratefully acknowledged. NMH gratefully acknowledges an IMPRS fellowship. This work was also supported by the European Research Council (ERC-2015-AdG694097), the Cluster of Excellence (AIM), Grupos Consolidados (IT1249-19) and SFB925 ”Light induced dynamics and control of correlated quantum systems. The Flatiron Institute is a division of the Simons Foundation.

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