Matrix-Isolation Study of the Reaction of Carbon Atoms with Chlorine. The Electronic and Vibrational Spectra of the Free Radical CCl2

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Abstract
Studies of the photolysis of N3CN in the presence of Cl2 in Ar and N2 matrices at 14°K provide evidence for the formation of the free radical CCl2 by the reaction of photolytically produced C atoms with Cl2. The two stretching fundamentals of CCl2 appear at 721 and 748 cm−1. The corresponding fundamentals of 13CCl2 have also been observed. When the sample is warmed above about 30°K, these features disappear, and CCl4 features grow in intensity, indicating that CCl2 can react with Cl2 with little or no activation energy. The valence angle of CCl2 probably lies between 90° and 110°. A weak band system appearing between 4400 and 5600 Å, with an average band separation of 305 cm−1, may also be attributed to CCl2. Analogy with the electronic absorption spectrum of CF2 suggests that CCl2 possesses a ground singlet state and that this band system arises from a transition between the ground‐state electronic configuration and the first excited electronic configuration of CCl2, involving an extensive progression in the upper‐state bending vibration.

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