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Frequency domain nonlinear spectroscopies are a useful probe of linear and non-linear transitions in a variety of biological, chemical, and materials systems. They require scanning of optical parametric amplifiers (OPAs). Each OPA contains multiple motors that move to prerecorded positions to optimize output at each desired color. OPA optimization and color accuracy are crucial for frequency domain experiments, where OPA color is scanned. Such performance is highly sensitive to environmental fluctuations, so motor positions must be regularly optimized and tuned. Despite the widespread availability of motorized OPAs, this frequent maintenance can make frequency domain spectroscopy a cumbersome and time-consuming process. We have found that fully automated approaches to tuning are invaluable when scanning OPAs. Here, we report four algorithms that accurately and robustly tune a variety of ultrafast laser systems—picosecond and femtosecond, homebuilt and commercial OPAs. Using case studies from previously published work, we illustrate how these four algorithms can be combined to tune all motors of an ultrafast laser system. These algorithms are available through open-source software and can be applied to existing instruments, significantly lowering the threshold for executing frequency domain spectroscopy. 

Nonlinear, four-wave mixing vibrational spectroscopies are commonly used to probe electron–vibration coupling in isotropic media. Most of these methods rely on infrared and/or Raman transitions, but methods involving hyper-Raman transitions are also possible. Hyper difference frequency generation (HDFG) spectroscopy is an underdeveloped four-wave mixing vibrational spectroscopy based upon both infrared absorption and hyper-Raman scattering transitions. Despite several experimental reports on HDFG, its spectroscopic properties have not been fully explored. To this end, we investigate the selection rules and behavior of HDFG spectroscopy as an upconverted infrared spectroscopy and as a probe of vibronic coupling in molecular systems. We discuss the similarities between HDFG, a four-wave mixing technique, and vibrational sum frequency generation (vSFG) spectroscopy, a three-wave mixing technique. vSFG and HDFG appear to provide similar output intensities, making HDFG feasible for vSFG practitioners. HDFG is shown to be a sensitive probe of vibronic coupling in bulk systems and provides an alternative method to investigate electronic-nuclear coordinate correlations. 

Vibrational fingerprints and combination bands are a direct measure of couplings that control molecular properties. However, most combination bands possess small transition dipoles. Here we use multiple, ultrafast coherent infrared pulses to resolve vibrational coupling between CH3CN fingerprint modes at 918 and 1039 cm(-1) and combination bands in the 2750-6100 cm(-1 )region via doubly vibrationally enhanced (DOVE) coherent multidimensional spectroscopy (CMDS). This approach provides a direct probe of vibrational coupling between fingerprint modes and near-infrared combination bands of large and small transition dipoles in a molecular system over a large frequency range.