Distinguishing Resonant from Non-Resonant Nonlinear Optical Processes Using Intensity-Intensity Correlation Analyses.

Three-color coherent anti-Stokes Raman scattering (CARS) represents non-degenerate four wave mixing that includes both non-resonant and resonant processes, the contributions of which depend upon how the molecular vibrational modes are being excited by the input laser pulses. The scattering signal due to resonant processes builds up progressively. An advanced analytical tool to reveal this deferred resonant signal buildup phenomenon is in need. In this work, we adapt a quantitative analytical tool by introducing one-dimensional and two-dimensional intensity-intensity correlation functions in terms of a new variable (probe pulse delay) and a new perturbation parameter (probe pulse linewidth). In particular, discrete diagonal directional sums are defined here as a tool to reduce both synchronous and asynchronous two-dimensional correlation spectroscopy (2D-COS) maps down to one-dimensional plots while maintaining the valuable analytical information. Detailed analyses using the all-Gaussian coherent Raman scattering closed-form solutions and the representative experimental data for resonant and non-resonant processes are presented and compared. The present work holds a promising potential for industrial application, e.g., by extractive industries to distinguish hydrocarbons (chemically resonant substance) from water (non-resonant contaminant) by utilizing the one- and two-dimensional correlation analyses.