Fundamental Aspects of Ionic Dissociations: The Fragmentation Pathways of Excited Bicyclobutane Cations

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Abstract
A most recently developed method to quantify the fragmentation pathways of excited radical cations is presented. Using bicyclobutane cation as an illustrative example, the RRKM analysis of the breakdown diagram determined by He‐Iα photoelectron‐photoion coincidence spectroscopy is outlined. The results imply complete isomerization to 1,3‐butadiene cation preceding the dissociative processes. The rate‐energy functions of four competitive primary fragmentation reactions, leading to C3H, C4H, C4H and C2H are established. There is compelling evidence that the production of C2H fragment ions does not compete effectively with these four reactions. The extent of kinetic and competitive shift effects is determined. The derived enthalpies of formation are in excellent accord with the available high quality reference data. The relative importance of different fragmentation pathways which ultimately lead to fragment ions of identical mass to charge ratio is assessed.