Matrix isolation study of the products of the interaction of electrons and metastable argon atoms with HCCl2F

Two groups of infrared absorptions common to experiments in which samples of HCCl₂ isolated in an argon matrix at 14 K are exposed to vacuum ultraviolet radiation or to electrons produced by ultraviolet irradiation of an alkali metal, as well as to experiments in which the Ar:HCCl₂F sample is codeposited with a beam of argon atoms excited in a microwave discharge, have been assigned to anions produced upon associative and dissociative electron capture by HCCI₂F. Detailed isotopic substitution studies suggest that these anions are (Cl₂C)H?F^?, representing a unique type of hydrogen bonding, and HCCIF^?. The HCClF^? anion photodecomposes in the 345–250nm spectral region, but the products of its photodecomposition have not been identified. Both CCl₂ and Cl₂CF are also produced in the discharge experiments, but there is no evidence for the production of HCF. Mechanisms for the formation of ion products by electron capture and by exposure of HCCl₂F to radiation or to excited argon atoms of energy equal to or less than 11.8 eV are considered.