Role of Metastable Dicationic Intermediates in the Breakup of CH$_4^{2+}$

Abstract

We investigate the fragmentation dynamics of methane dication (CH$_4^{2+}$) produced in collisions with 50-MeV C$^{6+}$ ions using the COLTRIMS technique. The method provides complete three-dimensional momentum vectors of the charged fragments, enabling full kinematic reconstruction of the fragmentation process. The dynamics are analyzed using Dalitz plots, Newton diagrams, and the native-frame method to distinguish between concerted and sequential dissociation mechanisms. The data indicate the presence of sequential fragmentation pathways for the CH$_4^{2+}$ $\rightarrow$ CH$_2^+$ + H$^+$ + H, CH$_4^{2+}$ $\rightarrow$ CH$^+$ + H$^+$ + 2H, and CH$_4^{2+}$ $\rightarrow$ C$^+$ + H$^+$ + 3H channels, consistent with dissociation via short-lived dicationic intermediates CH$_3^{2+}$, CH$_2^{2+}$, and CH$^{2+}$, respectively. From the Newton-diagram momentum distributions, we further estimate the half-rotational periods of the intermediate states, providing insight into their rotational dynamics and finite lifetimes prior to fragmentation. The experimental observations are further supported by comparisons with calculated potential-energy curves.