Oligoperoxides, H[OO(CH3)2C]nOOH, are formed as side products in the synthesis of the primary high explosive triacetone triperoxide (TATP). Previous tandem mass spectrometry (MSn ) experiments using a quadrupole ion trap reported that the openchained oligoperoxide adducts of ammonium or sodium resulted in different product ions in the mass spectra. Dissociation mechanisms were previously proposed based on MSn experiments, where n > 2; however, a dissociation pathway achieved by an MSn experiment, where n > 2, may not necessarily be the same pathway achieved in an MS2 experiment. For this dissertation research, the collision induced dissociation pathways were investigated for the open-chained oligoperoxides in MS2 experiments utilizing a quadrupole ion trap. Tandem mass spectral experiments were performed for the openchained oligoperoxides ranging from the trimer to the octamer (n=3-8), including both ammonium and sodium adducts. The dissociation pathways were proposed as a result of two-dimensional correlation spectroscopy applied to the mass spectral data, which was referred to as two-dimensional correlation mass spectrometry (2D-CMS). The 2DCMS method was first validated by analysis of simple and more complex kinetic models followed by simple and more complex molecules. To further aid in the elucidation of the dissociation mechanisms, computational chemistry was performed for the optimization of stable precursor and product ion structures and calculations of their relative energies and adduct dissociation energies.