Studying Stimulated Raman Activity in Surface-Enhanced Femtosecond Stimulated Raman Spectroscopy by Varying the Excitation Wavelength.

We present the first multiwavelength surface-enhanced femtosecond stimulated Raman spectroscopy (SE-FSRS) study, as well as the first observation of anti-Stokes vibrational features in SE-FSRS spectra. We compare stimulated Raman loss (SRL) and stimulated Raman gain (SRG) signals at three pump wavelengths chosen to sample different portions of nanoparticle aggregate localized surface plasmon resonances. The SE-FSRS signals exhibit similar signal magnitudes in the SRL or SRG regions of the spectra regardless of Raman pump or probe wavelength. The spectral lineshapes, however, differ dramatically with excitation wavelengths. The observed trends in spectral line shape show a strong dependence on the relative position of the excitation fields with respect to the plasmon resonance but do not match predictions from any existing SE-FSRS theory. These results suggest the need for further theoretical efforts with complementary experimental studies of individual aggregates to remove the effects of inherent ensemble averaging.