Chlorine-carbon bond cleavage in chloroacetyl chloride induced by low-energy (< 8 eV) electrons: Theoretical and...

Despite their toxicity and environmental impact, chlorinated compounds remain indispensable to modern industry. Although their complete replacement is improbable, innovation in processes, e.g., activation of carbon-chlorine (C-Cl) bonds, could redefine how they may be used. Chloroacetyl chloride (CAC), in particular, serves as a versatile building block in numerous chemical syntheses. Here, we investigate the interaction of CAC with low-energy (<8 eV) electrons. At these energies, resonant processes are responsible for the molecular fragmentation leading to the C-Cl bond cleavage as the predominant dissociation channel. The agreement between density functional theory (DFT) calculations, earlier results [Hacaloglu et al., J. Phys. Chem. 94, 4412-4415 (1990)], and the revisited experimental observations confirms the reliability of the theoretical approach. The gained information may contribute to the development of electron-based methods for chemical synthesis.