A new approach to vibrational sum frequency generation spectroscopy using near infrared pulse shaping.

We have developed a multipurpose vibrational sum frequency generation (vSFG) spectrometer that is uniquely capable of probing a broad range of chemical species, each requiring different experimental conditions, without optical realignment. Here, we take advantage of arbitrary near infrared (NIR) waveform generation using a 4f-pulse shaper equipped with a 2D spatial light modulator (SLM) to tailor upconversion pulses to meet sample dependent experimental requirements. This report details the experimental layout, details of the SLM calibration and implementation, and the intrinsic benefits/limitations of this new approach to vSFG spectroscopy. We have demonstrated the competency of this spectrometer by achieving an ∼3-fold increase in spectral resolution compared to conventional spectrometers by probing the model dimethyl sulfoxide/air interface. We also show the ability to suppress nonresonant background contributions from electrode interfaces using time delayed asymmetric waveforms that are generated by the NIR pulse shaper. It is expected that this advancement in instrumentation will broaden the types of samples researchers can readily study using nonlinear surface specific spectroscopies.