High resolution coherent three dimensional spectroscopy of NO2

Expansion from coherent 2D spectroscopy to coherent 3D spectroscopy can provide significant advantages when studying molecules that have heavily perturbed energy levels. This paper illustrates such advantages by demonstrating how high resolution coherent 3D (HRC3D) spectroscopy can be used to study a portion of the visible spectrum of nitrogen dioxide. High resolution coherent 2D spectra usually contain rotational and vibrational patterns that are easy to analyze, but severe congestion and complexity preclude its effective use for many parts of the NO2 spectrum. HRC3D spectroscopy appears to be much more effective; multidimensional rotational and vibrational patterns produced by this new technique are easy to identify even in the presence of strong perturbations. A method for assigning peaks, which is based upon analyzing the resulting multidimensional patterns, has been developed. The higher level of multidimensionality is useful for reducing uncertainty in peak assignments, improving spectral resolution, providing simultaneous information on multiple levels and states, and predicting, verifying, and categorizing peaks.