Optimized reconstructions of compressively sampled two-dimensional infrared spectra.

Abstract

Compressive sampling has the potential to dramatically accelerate the pace of data collection in two-dimensional infrared (2D IR) spectroscopy. We have previously introduced the Generic Iteratively Reweighted Annihilating Filter (GIRAF) reconstruction algorithm to solve the reconstruction in 2D IR compressive sampling. Here, we report a thorough assessment of this method and comparison to our earlier efforts using the Total Variation (TV) algorithm. We show that the GIRAF algorithm has some distinct advantages over TV. Although it is no better or worse in terms of ameliorating the impacts of compressive sampling on the measured 2D IR line shape, we find that the nature of those effects is different for GIRAF than they were for TV. In addition to assessing the impacts on the line shape of a single oscillator, we also test the ability of the algorithm to reconstruct spectra that have transitions from more than one oscillator, such as the coupled carbonyl oscillators in rhodium dicarbonyl. Finally, and perhaps most importantly, we show that the GIRAF algorithm has a distinct denoising effect on the signal-to-noise ratio (SNR) of the 2D IR spectra that can increase the SNR by as much as 4× without any additional signal averaging and collecting fewer data points, which should further enhance the acceleration of data collection that can be achieved using compressive sampling and enable even more challenging experimental measurements.