Quantification of Nuclear Coordinate Activation on Polaritonic Potential Energy Surfaces

TL;DR

This paper introduces a quantitative method using resonance Raman analysis to understand and control how polaritonic states influence nuclear displacements and chemical reactivity, enabling better design of cavity-controlled reactions.

Contribution

It provides a novel quantitative approach to analyze mode-specific nuclear displacements in polaritonic systems, aiding in the design of effective polaritonic catalysts.

Findings

Coupling alters the potential energy landscape significantly.

Cavity parameters can steer vibronic wavepackets selectively.

The method enables screening of polaritonic catalysts effectively.

Abstract

Polaritonic states, which arise from strong coupling between light and matter, show great promise in modifying chemical reactivity. However, reproducible enhancement of chemical reactions with polaritons is challenging due to a lack of understanding on how to launch wavepackets along productive reactive coordinates while avoiding unproductive local minima in the multidimensional potential energy landscape. Here we employ resonance Raman intensity analysis to quantify mode-specific nuclear displacement values in pentacene thin films and pentacene exciton-polaritons. We find that coupling significantly changes the potential energy landscape, including both enhancement and suppression of nuclear displacements. We demonstrate that controlling cavity parameters enables selective steering of vibronic wavepackets. Our approach provides a quantitative methodology for screening polaritonic catalysts and opens new avenues for designing reproducible and effective cavity-controlled chemistry.