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

Abstract

In this study, we explore the possibility of modulating product selectivity (branching ratios) in post-transition-state bifurcation reactions via vibrational strong coupling (VSC) to an optical cavity. Detailed classical and quantum dynamical calculations on a model potential reveal that the branching ratio can be enhanced by nearly a factor of two under VSC conditions. Interestingly, upon altering the shape of the potential, we find a switch in the cavity frequency at which maximum enhancement in selectivity is observed. Apart from emphasizing the role of both cavity-system and intramolecular energy transfer to the observed enhancements, we highlight the complexity of the VSC mechanism in terms of the choice of the cavity frequency vis-à-vis the various molecular mode frequencies. Our work shows that, in principle, cavity quantum electrodynamics can reshape dynamical outcomes in reactions with complex potential energy landscapes.