Quantum Mechanical Description of Raman Scattering from Molecules in Plasmonic Cavities.

Plasmon-enhanced Raman scattering can push single-molecule vibrational spectroscopy beyond a regime addressable by classical electrodynamics. We employ a quantum electrodynamics (QED) description of the coherent interaction of plasmons and molecular vibrations that reveal the emergence of nonlinearities in the inelastic response of the system. For realistic situations, we predict the onset of phonon-stimulated Raman scattering and a counterintuitive dependence of the anti-Stokes emission on the frequency of excitation. We further show that this QED framework opens a venue to analyze the correlations of photons emitted from a plasmonic cavity.