Abstract
The reaction of Br 2 with OClO is a self-propagating chain reaction which emits red and near infrared chemiluminescence (λ & >; 600 nm) owing to the B 3Π(0 +)−X 1Σ + transition of BrCl. The rate-controlling step ▪ is followed by reactions of BrO and ClO radicals that propagate the chain. Based on the steady state vibrational distribution determined for the B–X band system, electronically excited BrCl* (B) is believed to be formed in the reaction ▪ The overall photon yield Φ of BrCl chemiluminescence from the Br 2 + OClO reaction was found to exceed 3 × 10 −3. Typical steady state BrCl* concentrations were about 3 × 10 7 molecule cm −3 using [OClO] 0 = [Br 2] 0 = 2.3 × 10 13 molecule cm −3. A partial rotational analysis of the B–X spectrum of BrCl has resulted in new spectroscopic constants for the ground and excited states of 81Br 35Cl and of 79Br 35Cl.
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