Effect of reagent electronic excitation on the chemical reaction Br(2P1/2,3/2)+HI

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Abstract
Br(2P3/2)+HI are found to react at room temperature to give HBr+I(2P3/2) with a rate constant of (1.0±0.3) ×10−11 cm3 molecule−1⋅sec−1. For Br+HI, electronic excitation of Br inhibits the reaction to HBr+I. Collisions with HI remove excited Br(2P1/2) with a rate of about 0.25×10−11 cm3 molecule−1⋅sec−1. This rate includes electronic quenching and electronic‐to‐vibration energy transfer as well as reaction. From correlation arguments the reaction of excited Br(2P1/2) with HI is expected to be much slower than that of ground state. The observed rate is comparable to that for quenching plus electronic‐to‐vibration transfer for Br(3P1/2) by HCl and HBr.