Analyzing ultrafast multiplex coherent anti‐Stokes Raman spectra with picosecond probing

This article reports an efficient method to simulate time and frequency resolved coherent anti‐Stokes Raman scattering spectra measured with picosecond pump and probe fields and ultrashort Stokes pulses. A systematic comparison of measured and simulated time and frequency dependent data is presented for carbon tetrachloride, chloroform, cyclohexane, octane, and poly(methyl methacrylate). While the first compound exhibits no Raman active modes in the considered spectral region of the CH‐stretch vibrations, the other ones show Raman spectra of increasing complexity. Vibrational frequencies and homogeneous dephasing rates are extracted by fitting explicit analytical formulas to the recorded data. Interference between nonresonant and resonant contributions to the nonlinear polarization is taken fully into account. The ability to measure the influence of inhomogeneous broadening is discussed. Copyright © 2014 John Wiley & Sons, Ltd.