A perspective on ab initio modeling of polaritonic chemistry: The role of non-equilibrium effects and quantum collectivity

This Perspective provides a brief introduction into the theoretical complexity of polaritonic chemistry, which emerges from the hybrid nature of strongly coupled light-matter states. To tackle this complexity, the importance of ab initio methods is highlighted. Based on those, novel ideas and research avenues are developed with respect to quantum collectivity, as well as for resonance phenomena immanent in reaction rates under vibrational strong coupling. Indeed, fundamental theoretical questions arise about the mesoscopic scale of quantum-collectively coupled molecules when considering the depolarization shift in the interpretation of experimental data. Furthermore, to rationalize recent findings based on quantum electrodynamical density-functional theory (QEDFT), a simple, but computationally efficient, Langevin framework is proposed based on well-established methods from molecular dynamics. It suggests the emergence of cavity-induced non-equilibrium nuclear dynamics, where thermal (stochastic) resonance phenomena could emerge in the absence of external periodic driving. Overall, we believe that the latest ab initio results indeed suggest a paradigmatic shift for ground-state chemical reactions under vibrational strong coupling from the collective quantum interpretation toward a more local, (semi)-classically and non-equilibrium dominated perspective. Finally, various extensions toward a refined description of cavity-modified chemistry are introduced in the context of QEDFT, and future directions of the field are sketched. (C) 2022 Author(s).All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY)license (http://creativecommons.org/licenses/by/4.0/).

Automated summary

This article provides a brief introduction to the theoretical complexity of polaritonic chemistry and emphasizes the importance of ab initio methods. It proposes novel ideas and research avenues regarding quantum collectivity and resonance phenomena in reaction rates under vibrational strong coupling. A computationally efficient Langevin framework based on quantum electrodynamical density-functional theory is also suggested, revealing cavity-induced non-equilibrium nuclear dynamics. Overall, the latest ab initio results suggest a paradigmatic shift in the understanding of ground-state chemical reactions under vibrational strong coupling.