Laser induced fluorescence detection of CF, CF2 and CF3 in the infrared multiphoton dissociation of C3F6

Shock Wave Study of the Thermal Dissociations of C3F6and c-C3F6. I. Dissociation of Hexafluoropropene

“…A yield of 3 CF 2 per C 3 F 6 decomposed could be explained by reaction followed by the fast decomposition of C 2 F 4 . However, because there is evidence for contributions from reactions – (see refs − , , and), the reduction of the CF 2 yield may also be due to a more complex mechanism involving these reactions, see below. By working behind incident shock waves, we could investigate lower bath gas concentrations.…”

“…Branching fractions of 0.42:0.41:0.17, respectively, were determined. Complementary to this work were studies of the IR multiphoton dissociation , in which CF 3 CF (or C 2 F 4 ), CF 2 , and CF 3 were identified as primary dissociation products with branching fractions of CF 2 :CF 3 of 0.8:0.2. Assuming that the dissociation in both cases takes place from vibrationally highly excited electronic ground state molecules, these products were attributed to the channels normalC 3 normalF 6 → CF 3 CF + CF 2 goodbreak0em2em⁣ normalΔ H 0 ° ≈ 104 .25em kcal mol − 1 normalC 3 normalF 6 → CF 3 CFCF + normalF goodbreak0em2em⁣ normalΔ H 0 ° ≈ 124 .25em kcal mol − 1 normalC 3 normalF 6 → CF 3 + normalC 2 normalF 3 goodbreak0em2em⁣ normalΔ H 0 ° = 109.8 .25em kcal mol − 1 …”

“…Branching fractions of 0.42:0.41:0.17, respectively, were determined. Complementary to this work were studies of the IR multiphoton dissociation 2,3 in which CF 3 CF (or C 2 F 4 ), CF 2 , and CF 3 were identified as primary dissociation products with branching fractions of CF 2 :CF 3 of 0.8:0.2. Assuming that the dissociation in both cases takes place from vibrationally highly excited electronic ground state molecules, these products were attributed to the channels…”

The Stereochemistry of the Thermal Cheletropic Decarbonylation of 3-Cyclopentenone As Determined by Multiphoton Infrared Photolysis/Thermolysis

“…MP-IR decompositions of a number of systems have been reported. [28][29][30][31][32][33][34][35][36][37][38] Of the most relevance to the current work, MP-IR thermolysis of cyclobutyl acetate yields cyclobutene, while pyrolysis gives only butadiene as the product of secondary thermolysis of cyclobutene. 39 Thus, we anticipated that the reaction scheme for the MP-IR photolysis/thermolysis of 4 would be as in eq 2.…”

VUV photoabsorption by hexafluoropropene

“…However, a number of works focused on the ionisation and dissociation of hexafluoropropene have proved instructive for the assignment of absorption bands. Rubio et al [21] report the successful use of laser induced fluorescence to detect CF, CF 2 and CF 3 radicals formed by infrared multiphoton dissociation. Further hexafluoropropene infrared multiphoton dissociation studies [22,23] show CF 2 to be the most easily formed radical, whilst CF 3 production is weak.…”