Frequency comb SFG: a new approach to multiplex detection.

Determination of molecular orientation at interfaces by vibrational sum frequency generation spectroscopy (VSFG) requires measurements using at least two different polarization combinations of the incoming visible, IR, and generated SFG beams. We present a new method for the simultaneous collection of different VSFG polarization outputs by use of a modified 4f pulseshaper to create a simple frequency comb. Via the frequency comb, two visible pulses are separated spectrally but aligned in space and time to interact at the sample with mixed polarization IR light. This produces two different VSFG outputs that are separated by their frequencies at the monochromator rather than their polarizations. Spectra were collected from organic thin films with different polarization combinations to show the reliability of the method. The results show that the optical arrangement is immune to fluctuations in laser power, beam pointing, and IR spectral shape.

Optical Interference Enhances Nonlinear Spectroscopic Sensitivity: When Light Gives You Lemons, Model Lemonade.

Optical interference effects can be a nuisance in spectroscopy, especially in nonlinear experiments in which multiple incoming and outgoing beams are present. Vibrational sum frequency generation is particularly susceptible to interference effects because it is often applied to planar, layered materials, driving many of its practitioners to great lengths to avoid signal generation from multiple interfaces. In this perspective, we take a positive view of this metaphorical "lemon" and demonstrate how optical interference can be used as a tool to extract subtle changes in interfacial vibrational spectra. Specifically, we use small frequency shifts at a buried interface in an organic field-effect transistor to determine the fractional charge per molecule during device operation. The transfer matrix approach to nonlinear signal modeling is general and readily applied to complex layered samples that are increasingly popular in modern studies. More importantly, we show that a failure to consider interference effects can lead to erroneous interpretations of nonlinear data.