Comparison of the Raman detection limit for IRS- and CARS-spectroscopy at excitation near molecular one-photon resonance

The nonlinear Raman methods IRS and CARS are compared according to the signal detectability at excitation of molecules under the condition of one-photon resonance. At one photon resonance it is the background contribution resulting from the scattering molecules themselves that determines the maximum attainable signal to noise ratio. These contributions acting for IRS and CARS respectively are compared. The essential difference between IRS and CARS results from a 3rd order saturation contribution to IRS, which may mask the IRS Raman signal near exact resonance while it does not contribute to CARS. This gives to CARS the preference before IRS at resonance excitation. The situation for IRS with respect to background is similar to that of spontaneous Raman scattering, where the resonance fluorescence — corresponding to the saturation contribution at IRS — masks the resonance Raman signal.