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.
@article{arxiv.1906.02651,
title = {Exact Potential Energy Surface for Molecules in Cavities},
author = {Lionel Lacombe and Norah M. Hoffmann and Neepa T. Maitra},
journal= {arXiv preprint arXiv:1906.02651},
year = {2019}
}