The combination reaction of mercury atoms with bromine atoms from the direct photolysis of CF3Br has been studied. The kinetics were followed by monitoring the band intensities of the Π3/2−22Σ and Π1/2−22Σ systems of the HgBr transient with kinetic absorption spectroscopy. The Π1/2−22Σ system has been analyzed and the following constants obtained: Te = 34 741 cm−1, ωe″ = 188 cm−1, and ωe′ = 274 cm−1. The extinction coefficient of the 2875-Å band of the Π1/2−22Σ system has been found to have the value 1.2 × 104 mole−1·cm−1. The second-order rate constant for the reaction is 1.7 × 108 mole−1·sec−1 in 200 torr CF3Br and is independent of temperature between 120 and 175°C. The rate constant for the removal of HgBr which is second order in [HgBr] is 1.25 ± 0.8 × 1010 mole−1·sec−1 in the same mixture.
Ultraviolet absorption spectra were recorded for CdBr, CdI, ZnBr, and ZnI produced in the cophotolysis of the appropriate trifluoromethyl halide and dimethyl metal compounds. Both the Π3/22 − 2Σ andΠ1/22 − 2Σ systems were observed in all cases. Most of the bands analyzed are in agreement with the emission spectra reported earlier in the literature. The Π1/22 − 2Σ system of CdBr and ZnI are reported here for the first time. Complete vibrational analysis of the spectra was performed and the Π2 splitting values compared.
The combination reaction of mercury atoms with iodine atoms from the direct photolysis of CF3I has been studied. The 2π1/2−2Σ system of the HgI transient was observed by kinetic absorption spectroscopy, and analysis of this system led to the following constants: Te = 32 732 cm−1, ωe′ = 236 cm−1, and ωe″ = 125.5 cm−1. A value of 3538 cm−1 was obtained for the doublet splitting. This value is compared with those found for the other mercury halide diatomics, and the nature of the transition involved is discussed.
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