Molecular Ionization Dissociation Induced by Interatomic Coulombic Decay in an ArCH_{4}-Electron Collision System.

Abstract

Interatomic Coulombic decay (ICD) is a significant fragmentation mechanism observed in weakly bound systems. It has been widely accepted that ICD-induced molecular fragmentation occurs through a two-step process, involving ICD as the first step and dissociative-electron attachment (DEA) as the second step. In this study, we conducted a fragmentation experiment of ArCH_{4} by electron impact, utilizing the coincident detection of one electron and two ions. In addition to the well-known decay pathway that induces pure ionization of CH_{4}, we observed a new channel where ICD triggers the ionization dissociation of CH_{4}, resulting in the cleavage of the C-H bond and the formation of the CH_{3}^{+} and H ion pair. The high efficiency of this channel, as indicated by the relative yield of the Ar^{+}/CH_{3}^{+} ion pair, agrees with the theoretical prediction [L. S. Cederbaum, J. Phys. Chem. Lett. 11, 8964 (2020).JPCLCD1948-718510.1021/acs.jpclett.0c02259; Y. C. Chiang et al., Phys. Rev. A 100, 052701 (2019).PLRAAN2469-992610.1103/PhysRevA.100.052701]. These results suggest that ICD can directly break covalent bonds with high efficiency, bypassing the need for DEA. This finding introduces a novel approach to enhance the fragmentation efficiency of molecules containing covalent bonds, such as DNA backbone.