Cavity molecular dynamics of vibrational modes enhanced non-linear absorption and population dynamics

Abstract

We present a quantum description of SERRS, in analogy to the energy spectrum dynamics for a system that comprises two molecules interacting with a single plasmonic cavity, taking into account the effect of molecular vibrations and Van der Waals interactions between the two molecules. It is shown that the splitting of the transparency peak can easily distinguish two adjacent molecules with similar chemical structures and nearly equal vibrational frequencies. We also found that vibrational pumping can selectively activate a particular vibrational mode, thus providing a mechanism to control its population dynamics and drives plasmon-assisted chemistry. Our results will provide a new approach for understanding the role of cavity photons in a two-level system comprising interacting polaritons and phonons.