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 (PTSB) 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.

Accepted in J. Chem. Phys