We present a novel setup to elucidate the dynamics of interfacial molecules specifically, using surface-selective femtosecond vibrational spectroscopy. The approach relies on a fourth-order nonlinear optical interaction at the interface. In the experiments, interfacial molecules are vibrationally excited by an intense, tunable femtosecond midinfrared (2500–3800 cm-1) pump pulse, resonant with the molecular vibrations. The effect of the excitation and the subsequent relaxation to the equilibrium state are probed using broadband infrared+visible sum frequency generation (SFG) light, which provides the transient vibrational spectrum of interfacial molecules specifically. This IR pump-SFG probe setup has the ability to measure both vibrational population lifetimes as well as the vibrational coupling between different chemical moieties at interfaces. Vibrational lifetimes of interfacial molecules are determined in one-dimensional pump-SFG probe experiments, in which the response is monitored as a function of the delay between the pump and probe pulses. Vibrational coupling between molecular groups is determined in two-dimensional pump-SFG probe experiments, which monitor the response as a function of pump and probe frequencies at a fixed delay time. To allow for one setup to perform these multifaceted experiments, we have implemented several instrumentation techniques described here. The detection of the spectrally resolved differential SFG signal using a combination of a charge-coupled device camera and a piezocontrolled optical scanner, computer-controlled Fabry–Pérot etalons to shape and scan the IR pump pulse and the automated sample dispenser and sample trough height corrector are some of the novelties in this setup.

Rev. Sci. Instrum.

Ghosh, A., Smits, M., Bredenbeck, J., Dijkhuizen, N., & Bonn, M. (2008). Femtosecond time-resolved and two-dimensional vibrational sum frequency spectroscopic instrumentation to study structural dynamics at interfaces. Rev. Sci. Instrum., 79(Article number: 93907), 1–9. doi:10.1063/1.2982058