Chemical Physics Letters, Vol.672, 112-118, 2017
Photochemistry of UV-excited trifluoroacetylacetone and hexafluoroacetylacetone II: Quantum yield and rate constants of hydrogen fluoride photoelimination forming fluorinated methylfuranones
The photochemistry of gas-phase 1,1,1-trifluoroacetylacetone (TFAA) and 1,1,1,5,5,5-hexafluoroacetylace tone (HFAA) excited with ultraviolet light involves a significant photoelimination channel producing HF and difluoromethylfuranone or pentafluoromethylfuranone, respectively. We report collisional self quenching of the experimentally-determined relative quantum yield, and determine rate constants of 0.27 +/- 0.03 and 0.33 +/- 0.04 mu s(-1), for HFAA and TFAA respectively. A strong collision model is consistent with the observed quenching. The data suggest that this elimination is the primary photochemical fate at low pressure in both cases. The TFAA rate constant is larger than that for HFAA, in spite of TFAA having half as many fluorine atoms as HFAA. (C) 2017 Elsevier B.V. All rights reserved.
Keywords:Unimolecular reaction;Photodissociation rate;Lifetime;Collisional quenching;Hydrogen bonding