Abstract
Time dependent quantum mechanical calculations of the photodissociation of C2F4IBr are reported. The calculations successfully model the experimental absorption spectra [W. H. Pence, S. L. Baughcum, and S. R. Leone, J. Phys. Chem. 85, 3844 (1981)] as well as the branching ratio of final products due to photodissociation [D. Krajnovich, L. J. Butler, and Y. T. Lee, J. Chem. Phys. 81, 3031 (1984)]. The model used consists of two degrees of freedom, an iodine and a bromine coordinate, and two diabatic potential energy surfaces which are repulsive in the iodine and bromine cordinates, respectively. The study gives a consistent picture of the experimental I:Br branching ratio at 266, 248, and 193 nm in terms of a crossing of diabatic potential energy surfaces. However, the same model requires an anomalously small surface coupling when applied to the related CH2IBr system to agree with experiment. The time dependent formulation of absorption spectroscopy and photodissociation is extended to systems with chemical branching, and a simple new technique for calculating frequency dependent chemical branching ratios from short time dynamics is presented.
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