Infrared chemiluminescence investigation of the reactions of halogen atoms with deuterated ethylene and benzene derivatives

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Abstract
The technique of arrested relaxation infrared chemiluminescence has been used to investigate the reactions of halogen atoms with various deuterated olefinic and aromatic compounds. From infrared emission spectra of the products, the vibrational energy distributions were measured and then compared to the distributions resulting from statistical partitioning of energy. The reactions studied here are reactions of fluorine atoms with ethylene‐d4, vinyl chloride‐d3, vinyl bromide‐d3, benzene‐d6, toulene‐d8, chlorobenzene‐d5, and bromobenzene‐d5 and the reaction of chlorine atoms with vinyl bromide‐d3. Nonstatistical product energy distributions were observed for the F+ethylene‐d4 and Cl+vinyl bromide‐d3 reactions. All other reactions showed a statistical distribution of energy among the modes that were observed. The mechanism of distribution of energy among vibrational modes in intermediate size molecules is discussed in relation to these results.