Isomerization Dynamics in the Symmetric and Asymmetric Fragmentation of Ethane Dications

Abstract

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 <i>ab initio</i> quantum chemical calculations demonstrate that the reaction pathway involving hydrogen-migration-induced isomerization of [CH₃-CH₃]²⁺ to [CH₂-CH₄]²⁺ can be accessed <i>via</i> 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.