A roadmap toward the theory of vibrational polariton chemistry

TL;DR

This paper reviews key experiments and theories in vibrational polariton chemistry, proposing a research roadmap to develop a comprehensive theoretical understanding of how strong light-matter coupling influences chemical reactions.

Contribution

It provides a critical analysis of existing theories and experimental results, and outlines future experimental and theoretical directions for the field.

Findings

Experimental evidence of reaction rate modification in cavities

Analysis of theories like quantum electrodynamics and vibrational energy redistribution

Proposed experiments to test and refine theoretical models

Abstract

The field of vibrational polariton chemistry was firmly established in 2016 when a chemical reaction rate at room temperature was modified within a resonantly tuned infrared cavity without externally driving the system. Despite intense efforts by scientists around the world to understand why the reaction rate changes, no convincing theoretical explanation exists. In this perspective, first, we briefly review this seminal experiment, as well as relevant experiments that have since followed that have hinted at the roles of reactant concentration, cavity frequency, and symmetry. Then, we analyze the relevance of leading theories, such as quantum electrodynamics-modified transition rate theories, the photonic solvent cage effect, the impact of dissipation from dark states, bond strengthening via intramolecular vibrational energy redistribution, and collectively enhanced local molecular properties. Finally, we construct a roadmap toward the theory of vibrational polariton chemistry by suggesting experiments to test theories and new paths for theorists. We believe that understanding the importance of the onset of the strong coupling regime, designing experiments to capture changes in reaction pathways, and further developing the theories of cavity-modified intramolecular vibrational energy redistribution and collectively enhanced local molecular properties are crucial next steps. We hope this perspective will be a valuable resource for guiding research in the field of vibrational polariton chemistry.