Abstract

Vibrationally excited /sup 14/CH/sub 3/CF/sub 3/ containing 102.8 +- 1.0 kcal mol/sup -1/ of excess energy has been produced via the photochemically initiated cross combination of /sup 14/CH/sub 3/ and CF/sub 3/ radicals in the gas phase. The samples contained dilute concentrations of /sup 14/CH/sub 3/CO/sup 14/CH/sub 3/ and CF/sub 3/COCF/sub 3/ photolysis precursors together with C/sub 2/H/sub 6/ or C/sub 2/F/sub 6/ host gases. The pressure dependences of the (/sup 14/CH/sub 2/= =CF/sub 2/:/sup 14/CH/sub 3/CF/sub 3/) decomposition-stabilization product ratios were measured for these host substances throughout the range 0.5 less than or equal to (D/S) less than or equal to 1000 and then compared with the stepladder, Gaussian, and exponential theoretical transition probability models. None of the model calculations accounted for the qualitative characteristics of the extended range data, so that mathematically unique energy transfer models and values could not be assigned.

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