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

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.