By using the sensitized phosphorescence spectroscopy, the intensity of the phosphorescence has been recorded upon excitation of the benzonitrile dimer to the S1 vibronic states in a free jet. The results indicate that the strong vibrational energy dependence of the fluorescence quantum yield, reported previously, is attributable to the increasing rate of intersystem crossing with increasing vibrational energy. Similar behavior is also observed in other van der Waals complexes of benzonitrile though the increase is less obvious. The enhancement of the intersystem crossing can be correlated with the state density of van der Waals modes in the S1 electronic state. In case of the benzonitrile trimer and benzonitrile-Kr complex, intersystem crossing is found to be fully efficient even without vibrational excitation.
Research on Chemical Intermediates – Springer Journals
Published: Apr 15, 2009
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