Absolute Cross Sections of Liquids from Broadband Stimulated Raman Scattering with Femtosecond and Picosecond Pulses.

Broadband stimulated Raman scattering (SRS) is often observed in applications that use nonlinear spectroscopy to probe the composition or dynamics of complex systems. Whether the SRS response is measured intentionally or unintentionally, as a background signal, the relative scattering intensities provide a quantitative measure of the population profile of target molecules. Solvent scattering is a valuable internal reference for determining absolute concentrations in these applications, but accurate cross sections have been reported for only a limited number of transitions in select solvents and were measured using spontaneous Raman scattering with narrowband continuous wave or nanosecond light sources. This work reports the measurement and analysis of absolute Raman scattering cross sections spanning the frequency range of 500-4000 cm-1 for cyclohexane, DMSO, acetonitrile, methanol, water, benzene, and toluene using broadband SRS with femtosecond and picosecond Raman pump pulses at 488 nm. Varying the duration of the Raman pump pulses from ∼80 fs to >1 ps confirms that the cross sections are independent of the spectral bandwidth across the range of ∼250 to <20 cm-1. The cross sections and depolarization ratios measured using broadband SRS agree with the limited number of previously reported values, after accounting for overlapping transitions in the lower-resolution femtosecond and picosecond spectra. The SRS cross sections reported here can be used with confidence as internal reference standards for a wide range of applications, including nonlinear spectroscopy and coherent microscopy measurements using ultrafast lasers.