Coherent electron-vibron interactions in Surface-Enhanced Raman Scattering (SERS)

Abstract: In this work we identify coherent electron-vibron interactions between near-resonant and non-resonant electronic levels that contribute beyond standard optomechanical models for off-resonant or resonance SERS. By developing an open-system quantum model using first molecular interaction principles, we show how the Raman interference of both resonant and non-resonant contributions can provide several orders of magnitude modifications of the SERS peaks with respect to former optomechanical models and over the fluorescence backgrounds. This cooperative optomechanical mechanism allows for generating an enhancement of nonclassical photon pair correlations between Stokes and anti-Stokes photons, which can be detected by photon-counting measurements. Our results demonstrate Raman enhancements and suppressions of coherent nature that significantly impact the standard estimations of the optomechanical contribution from SERS spectra and their quantum mechanical observable effects.