Vibrational line shape effects in plasmon-enhanced stimulated Raman spectroscopies.

A density matrix treatment of plasmon-enhanced (PE) stimulated Raman spectroscopies is developed. Specifically, PE stimulated Raman Gain/Loss (PE-SRG/L) and coherent anti-Stokes Raman scattering (PE-CARS) due to monochromatic excitation and PE femtosecond stimulated Raman spectroscopy (PE-FSRS) are considered. A Lorentz oscillator model is used to explicitly describe the time dependence of plasmon-enhanced optical fields. These temporal characteristics are required for a density matrix based description of all plasmon-enhanced nonlinear molecular spectroscopies. Dispersive vibrational line shapes in PE-SRG/L and PE-FSRS spectra are shown to result primarily from terms proportional to the square of the complex optical field enhancement factor. The dependence on the plasmon resonance, picosecond and femtosecond pulse characteristics, and molecular vibrational properties are evident in the density matrix derived PE-FSRS intensity expression. The difference in signal detection mechanisms accounts for the lack of dispersive line shapes in PE spontaneous Raman spectroscopy. This density matrix treatment of PE-FSRS line shapes is compared with prior coupled wave results.