Time-dependent density functional theory (TD-DFT) with different functional and related atomic basis sets, is applied to calculate the vertical transitions from the ground to the low-lying valence electronic excited states of hexafluoropropene in vacuum. The results are in satisfactory agreement with the recent high-resolution photoabsorption spectrum of hexafluoropropene in gas phase. The primary photodissociation channel was also studied and the binding energy of the weakest C-F bond of the molecule was determined. (C) 2004 Elsevier B.V. All rights reserved.