Abstract
The dissociation yield and branching ratio in CO/sub 2/-laser-induced multiphoton dissociation (MPD) of CF/sub 3/CF/sub 2/CHF/sub 2/ were studied as a function of irradiation frequency (979.7, 1037.4, and 1081.1 cm/sup -1/) and laser fluence (focal fluence .. C/sub 2/F/sub 5/ + CHF/sub 2/, and CF/sub 3/CF/sub 2/CHF/sub 2/ ..-->.. CF/sub 3/ + C/sub 2/HF/sub 4/) rather than via HF elimination (CF/sub 3/CF/sub 2/CHF/sub 2/ ..-->.. C/sub 3/F/sub 6/ + HF) in the authors experimental conditions. The observed branching ratio between the two C-C rupture channels (approx.2:1) agreed with the results obtained by RRKM calculation. A remarkable difference in product distribution with respect to the irradiation frequency was observed at higher laser fluences. This indicates that the secondary photolysis of primarily produced radicals within the laser pulse occurred significantly at highermore » fluences (i.e., C/sub 2/F/sub 5/ ..-->.. CF/sub 3/ + CF/sub 2/, CHF/sub 2/ ..-->..CF/sub 2/ + H, CF/sub 3/ ..-->.. CF/sub 2/ + F, and CHF/sub 4/ ..-->..CF/sub 2/ + CHF/sub 2/), depending strongly upon the irradiation frequencies.« less
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