Pulsed and steady-state photolysis techniques have been employed to measure the rate coefficients for collisional deactivation of the spin–orbit excited state of atomic bromine, Br(4 2P1/2). Pulsed lifetime studies for quenching by Br2 and CO2 yielded absolute rate coefficients at room temperature of kBr2=1.2±0.1×10−12 and kCO2=1.5±0.3×10−11 cm3/molecule s. The rate coefficients for quenching by rare gases, N2, O2, NO, NO2, N2O, CO, CO2, COS, SO2, SF6, CF4, CH4, H2S, H2, D2, HBr, HCl, and HI, relative to that for Br2 were determined in a steady-state photolysis experiment. Correlation of the deactivation probabilities with energy defect for the case of electronic-to-vibrational energy transfer is demonstrated.
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