Zooming in on vibronic structure by lowest-value projection reconstructed 4D coherent spectroscopy

A fundamental goal of chemical physics is an understanding of microscopic interactions in liquids at and away from equilibrium. In principle, this microscopic information is accessible by high-order and high-dimensionality nonlinear optical measurements. Unfortunately, the time required to execute such experiments increases exponentially with the dimensionality, while the signal decreases exponentially with the order of the nonlinearity. Recently, we demonstrated a non-uniform acquisition method based on radial sampling of the time-domain signal [W. O. Hutson et al., J. Phys. Chem. Lett. 9, 1034 (2018)]. The four-dimensional spectrum was then reconstructed by filtered back-projection using an inverse Radon transform. Here, we demonstrate an alternative reconstruction method based on the statistical analysis of different back-projected spectra which results in a dramatic increase in sensitivity and at least a 100-fold increase in dynamic range compared to conventional uniform sampling and Fourier reconstruction. These results demonstrate that alternative sampling and reconstruction methods enable applications of increasingly high-order and high-dimensionality methods toward deeper insights into the vibronic structure of liquids.