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arXiv · 1906.02651

Exact Potential Energy Surface for Molecules in Cavities

Lionel Lacombe·Norah M. Hoffmann·Neepa T. Maitra
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Abstract

We find and analyze the exact time-dependent potential energy surface driving the proton motion for a model of cavity-induced suppression of proton-coupled electron-transfer. We show how, in contrast to the polaritonic surfaces, its features directly correlate to the proton dynamics and discuss cavity-modifications of its structure responsible for the suppression. The results highlight the interplay between non-adiabatic effects from coupling to photons and coupling to electrons, and suggest caution is needed when applying traditional dynamics methods based on polaritonic surfaces.

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Lionel Lacombe, Norah M. Hoffmann, Neepa T. Maitra. 2019-06-06. Exact Potential Energy Surface for Molecules in Cavities. https://doi.org/10.1103/physrevlett.123.083201

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