Time-dependent band position difference between vibrational sum and difference frequency generation: a phenomenon originating from dispersion in the visible pulse.

Vibrational spectroscopy is significant for identifying chemical specification. Here, the spectral band frequencies corresponding to the same molecular vibration in sum frequency generation (SFG) and difference frequency generation (DFG) spectra present delay-dependent deviation. Through numerical analysis of time resolved SFG and DFG spectra with a frequency marker in the incident IR pulse, the frequency ambiguity was not caused by any structure and dynamic variation on the surface, but from the dispersion in the incident visible pulse. Our results provide a helpful method to correct the vibrational frequency deviation and improve the assignment accuracy for SFG and DFG spectroscopies.