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IR multiphoton photochemistry of CF/sub 3/Cl

Journal Article · · J. Chem. Phys.; (United States)
OSTI ID:6581832

CF/sub 3/Cl has been dissociated using the focused output of a CO/sub 2/ TEA laser operating on the R(40) line of the 9.6 mm band. IR fluorescence has been observed for HF and HCl after irradiating mixtures of CF/sub 3/Cl, HBr, and Ar, indicating the production of F as well as Cl. In addition, the laser-induced fluorescence spectrum of CF/sub 2/ has been observed using a KrF laser (249 nm) to excite the CF/sub 2/ A/sup 1/B/sub 1/reverse arrowX/sup 1/A/sub 1/ transition. A two step dissociation mechanism in which CF/sub 3/ and Cl are the primary products followed by the subsequent multiphoton absorption and dissociation of CF/sub 3/ to produce CF/sub 2/ and F is proposed. Evidence for secondary dissociation of CF/sub 3/ has been demonstrated by observing CF/sub 2/ in the infrared multiphoton dissociation of C/sub 2/F/sub 6/, which is known to produce CF/sub 3/ at low fluence. Further evidence in support of a two-step dissociation mechanism is given by analysis of stable products, fluence studies, and RRKM calculations.

Research Organization:
Department of Chemistry, Brookhaven National Laboratory, Upton, New York 11973
OSTI ID:
6581832
Journal Information:
J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 74:9; ISSN JCPSA
Country of Publication:
United States
Language:
English