Thermodynamic coupling of reactions via few-molecule vibrational polaritons

Abstract: Interaction between light and molecular vibrations leads to hybrid light-matter states called vibrational polaritons. Even though many intriguing phenomena have been predicted for single-molecule vibrational strong coupling (VSC), several studies suggest that these effects tend to be diminished in the many-molecule regime due to the presence of dark states. Achieving single or few-molecule vibrational polaritons has been constrained by the need for fabricating extremely small mode volume infrared cavities. In this work, we propose an alternative strategy to achieve single-molecule VSC in a cavity-enhanced Raman spectroscopy (CERS) setup, based on the physics of cavity optomechanics. We then present a scheme harnessing few-molecule VSC to thermodynamically couple two reactions, such that a spontaneous electron transfer can now fuel a thermodynamically uphill reaction that was non-spontaneous outside the cavity.