One of the most powerful tools to investigate the structural dynamics of electronically excited molecular systems is visible-pump/mid-infrared-probe spectroscopy. When performing this kind of experiments one must be aware of the artifacts deriving from the non-linear response of the solvent and of the sample cell itself. Cross-phase modulation (XPM) is observed when a strong visible-pump pulse modulates the refraction index seen by the mid-infrared-probe. The effect is enhanced when the probe pulse is chirped and causes the distortion of the transient signal in both the frequency and the time domains. We undertook a detailed simulation of XPM in the mid-infrared region where a visible pulse modulates the MIR pulse by XPM and in close conditions to the experimental ones. Our simulation takes into account the different group velocities of the pump and probe pulses and includes the influence of the linear chirp of the mid-infrared pulse and its asymmetry. The results of our numerical calculations fit very well the experimental signals measured in a 2 mm thick CaF2 window.
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