Vibrational strong coupling influences product selectivity in a model for post transition state bifurcation reactions

TL;DR

This study demonstrates that vibrational strong coupling (VSC) can significantly alter product selectivity in a model for post-transition state bifurcation reactions, revealing the complex influence of cavity parameters on reaction dynamics.

Contribution

It provides the first detailed dynamical analysis showing how VSC can enhance product branching ratios in bifurcation reactions, highlighting the role of cavity and molecular mode interactions.

Findings

VSC can nearly double product selectivity in the model system.

Classical and quantum dynamics show excellent agreement under certain conditions.

Cavity frequency relative to molecular modes critically affects reaction outcomes.

Abstract

Understanding the mechanism of chemical reaction rate modulation by vibrational strong coupling (VSC) has been the focus of several recent studies. However, a definitive explanation for the mode-specificity of VSC still eludes us. In this study, we highlight the dynamics under VSC by utilizing a model for post-transition state bifurcation (PTSB) reactions coupled to an optical cavity. The minimal two-dimensional PTSB model features a valley-ridge inflection (VRI) point leading to bifurcated energetically asymmetric product wells. Here, we are interested in exploring whether the product selectivity (branching ratios) in such PTSB systems, known to be sensitive to dynamical effects, can be significantly perturbed under VSC conditions. Detailed classical and quantum dynamical calculations, along with systematic variation of the model parameters, reveals that the branching ratio can be enhanced under VSC by nearly a factor of two. Interestingly, for certain parameter regimes we find excellent classical-quantum correspondence. Apart from emphasizing the role of both cavity-system and intramolecular energy transfer in the observed enhancements, our study brings out the complexity of VSC in terms of the choice of the cavity frequency vis--\`a--vis the various molecular mode frequencies. In addition, our work highlights the potential of cavity quantum electrodynamics as a tool for reshaping dynamical outcomes in reactions with complex potential energy landscapes.