Institution: | Physique des Interactions Ioniques et Moleculaires, UMR 6633, Equipe de Spectrométries et Dynamique Moléculaire, Boîte 542, Université de Provence, F-13397, Marseille Cedex 20, France |
Abstract: | IR spectroscopy was coupled with the matrix isolation technique to study the molecular complex formed between C3O2 and HCl and its photodissociation. The vibrational frequencies of the complex were compared with those of HCl and C3O2 monomers. For C3O2, a bent structure was characterized in the solid environment. The vibrational frequencies were calculated in the 4000–400 cm?1 range using an ab initio method at the MP2/6-31G** level for the most stable complex; these frequencies describe the hydrogen interaction with the central carbon atom of C3O2 (T complex). The measured shifts between the vibrational mode frequencies of the complex and monomers were in good agreement with the calculated values. Broad-band UV irradiation ( > 230 nm) of the T complex leads preferentially to ketene chloride and carbon monoxide. Ketene chloride formation can be explained by the reaction between HCl and the carbene C2O, which results from photo-dissociation at the C=CO bond of C3O2. |