Intramolecular Processes Revealed Using UV-Laser-Induced IR-Fluorescence: A New Perspective on the "Channel Three" of Benzene.

Radiative relaxation in the infrared (IR) is common following nonradiative electronic relaxation processes, but it is rarely measured. We present ultraviolet laser-induced infrared fluorescence (UV-LIIRF) excitation spectroscopy and dispersed UV-LIIRF spectroscopy of gas phase benzene vibronically excited around the onset of channel 3, using a homemade spectrometer. We found that the vibrational IR fluorescence yield is clearly higher when benzene is excited above the onset than when it is excited below. Significant changes in dispersed IR emission profiles resulting from excitations below and above the onset of channel 3 were also observed. These results suggest that isomerization of benzene toward fulvene occurs efficiently below the opening of channel 3 and confirm that channel 3 involves a photophysical relaxation pathway that efficiently competes with isomerization.