Journal of Chemical Physics, Vol.111, No.1, 100-107, 1999
Ultraviolet photodissociation of furan probed by tunable synchrotron radiation
The photodissociation dynamics of furan at 193 nm have been studied using photofragment translational spectroscopy with tunable vacuum ultraviolet (VUV) probe provided by synchrotron radiation on the Chemical Dynamics Beamline at the Advanced Light Source. Three primary channels are observed: HCO+C3H3, CO+C3H4, and H2CCO+C2H2. The evidence suggests that the two closed-shell channels occur on the ground-state potential energy surface (PES) following internal conversion, while the radical channel likely takes place on an excited PES. All channels exhibit a barrier for dissociation with the acetylene+ketene channel having the largest value at about 25 kcal/mol. Angular distribution measurements show anisotropy only for the radical channel. These findings are consistent with a rapid excited state dissociation for the radical channel and slow dissociation for the other two pathways. The two ground-state dissociation channels-propyne+CO and acetylene+ketene-should be important in the thermal decomposition of furan as was found in pyrolytic studies [A. Lifshitz, M. Bidani, and S. Bidani, J. Phys. Chem. 90, 5373 (1986)] and theoretical investigations [R. Liu, X. Zhou, and L. Zhai, J. Comput. Chem. 19, 240 (1998)].