Effects of Ring Fluorination on the Ultraviolet Photodissociation Dynamics of Phenol.

The dynamics of photoinduced O-H bond fission in five fluorinated phenols (2-fluorophenol, 3-fluorophenol, 2,6-difluorophenol, 3,4,5-trifluorophenol, and pentafluorophenol) have been investigated by H Rydberg atom photofragment translational spectroscopy following excitation at many wavelengths in the range 220 ≤ λ ≤ 275 nm. The presence of multiple fluorine substituents reduces the efficiency of O-H bond fission (by tunneling) from the first excited (11ππ*) electronic state, whereas all bar the perfluorinated species undergo O-H bond fission when excited at shorter wavelengths (to the 21ππ* state). As in bare phenol, O-H bond fission is deduced to occur by non-adiabatic coupling at conical intersections between the photoprepared "bright" ππ* states and the 11πσ* potential energy surface. In all cases, the fluorophenoxyl photoproducts are found to be formed in a range of vibrational levels, all of which include an odd number of quanta (typically one) in an out-of-plane (a″) vibrational mode; this product vibration is viewed as a legacy of the parent out-of-plane motions that promote non-adiabatic coupling to the dissociative 11πσ* potential. The radical products also show activity in in-plane vibrations involving coupled (both in- and out-of-phase) C-O and C-F wagging motions, which can be traced to the impulse between the recoiling O and H atoms and, in detail, are sensitive to the presence (or not) of an intramolecular F···H-O hydrogen bond. Upper limit values for the O-H bond dissociation energies are reported for all molecules studied apart from pentafluorophenol.