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| - Quenching of I(2P1/2) by Cl2 and Cl Atoms over the Temperature Range 297−663 K
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| - Time-resolved fluorescence measurements have been used to examine the quenching of I(2P1/2) by Cl2 and Clatoms. Pulsed photolysis of CF3I was used to generate I*. Quenching by Cl2 was examined using 248 nmphotolysis as Cl2 does not absorb significantly at this wavelength. Photolysis at 308 nm, which dissociatesboth CF3I and Cl2, was used to investigate quenching by Cl atoms. Quenching kinetics were characterizedover the temperature range from 297 to 663 K. The rate constant for quenching by Cl atoms was found to bealmost independent of temperature, whereas the rate constant for Cl2 increased by 3 orders of magnitude ingoing from 297 to 663 K. Theoretical calculations show that quenching by Cl atoms is mediated by a curvecrossing process. The temperature dependence of the Cl2 quenching rate constant is attributed to the reactivechannel I* + Cl2 → ICl + Cl(2P).
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