The first portion of this dissertation focuses on the velocity mapped imaging experiments that have been used to study the angular distribution of the products of nitric oxide predissociation following its excitation to the 11s, 10p, 11p and 9f Rydberg levels based on the NO+ (X 2[SIGMA]+ ) core. Ion dip spectra of the Rydberg states were recorded along with velocity-mapped images at the major peaks. Theory is presented based on previous analyses of Hund's coupling cases (a) and (b) and has been modified to include transitions to states of case (d) coupling. The reasonable agreement of the calculated and experimental anisotropy parameters [beta]2 and [beta]4 shows the predictive value of the theory. The second portion of this dissertation explores high resolution coherent multidimensional spectroscopy as an alternative to conventional methods for generating rotationally resolved electronic spectra of gas phase molecules. In addition to revealing information such as the relationships among peaks, it can provide clearly recognizable patterns for systems that otherwise appear patternless due to rotational congestion. These patterns depend upon the scanning strategy and the corresponding four wave mixing process. The background and theory necessary for using high resolution coherent 3D spectroscopy are presented, including pattern prediction and dependence upon rotational constants and quantum numbers. These tools are then applied to a detailed rotational-vibrational analysis of bromine gas.