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UBC Theses and Dissertations

Primary photochemical processes in hexafluorobiacetyl at 313 nm. Reid, William John


Absolute photochemical quantum yields of hexafluorobiacetyl have been obtained at 313 nm. over a range of pressures. These were correlated with absolute phosphorescence and fluorescence quantum yields which had been previously obtained in the same pressure range in order to further elucidate the primary process. A mechanism is proposed and the results are discussed in relation to it. The rate constants for singlet dissociation, for intersystem crossing from the level reached on excitation, and for triplet dissociation were found to be 0.7 x 10⁸ secˉ¹ , 0.6 x 10⁸ sec ˉ¹ and 1.3 x 10⁷ sec ˉ¹ , respectively. The fluorescence lifetime is estimated to be of the order of 2 nsec. above 40 torr.

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