An approach to compatible multiple nonlinear vibrational spectroscopy measurements using a commercial sum frequency generation system

Abstract

In this paper, we designed a compatible multiple nonlinear vibrational spectroscopy system that can be used for recording infrared–visible sum frequency generation vibrational spectra (SFG) and infrared–infrared–visible three-pump-field four-wave-mixing (IIV-TPF-FWM) spectra using a commercial EKSPLA SFG system. This is the first time IIV-TPF-FWM signals were obtained using picosecond laser pulses. We have applied this compatible system to study the surface and vibrational structures of riboflavin molecules (also known as vitamin B2). The SFG spectra of eight polarization combinations have non-vanishing signals. The signals with incoming s-polarized IR are relatively weaker than the signals with incoming p-polarized IR. Under the double resonant conditions, the SFG signals of the conjugated tricyclic ring are greatly enhanced. For the IIV-TPF-FWM spectra with incoming p-polarized IR, only the sspp and pppp polarization combinations have non-vanishing signals. The IIV-TPF-FWM spectra show a very strong peak at 1585 cm⁻¹ that is mainly dominated by the N₅–C_4a stretch. The method developed in this study will be helpful for researchers, either using a home-built or commercial (EKSPLA) SFG system, to obtain independent and complementary measurements for SFG spectroscopy and more detailed structural information of interfacial molecules.