Isomerization Dynamics in the Symmetric and Asymmetric Fragmentation of Ethane Dications.

Hydrogen- or proton-migration-induced isomerization has recently been of concern for its critical role in the dissociation of organic molecules of astrophysical or biological relevance. Herein we present a combined experimental and theoretical study of the two-body C-C bond breakdown dissociation of ethane dication. For the asymmetric fragmentation channel CH2+ + CH4+, the kinetic energy release measurements and ab initio quantum chemical calculations demonstrate that the reaction pathway involving hydrogen-migration-induced isomerization of [CH3-CH3]2+ to [CH2-CH4]2+ can be accessed via the lowest triplet state rather than the ground singlet state of ethane dication. Interestingly, it is found that a considerable proportion of the yield of symmetric fragmentation CH3+ + CH3+, which is usually considered from a direct Coulomb explosion and seemingly independent of isomerization, could come from the dissociation of ethane dication in the ground singlet state with the involvement of [CH3-CH3]2+ isomerization to intermediate [H2C(H2)CH2]2+ of the diborane-like double-bridged structure.