Discovery of the radical cations of van der Waals complexes and their stepwise photoinduced reactions

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Studies of molecular ions of van der waals (vdW) complexes in the gas phase are being developed with the advent of the free-jet expansion and the multiphoton ionization techniques. However, in condensed phase the corresponding study is scarce. In this research project some radical cations of vdW molecules in rigid solutions are newly found and their stepwise photoincduced reactions are studied. In particular, the system of benzene-ethylene in Freon matrices is studied extensively to find that the ionized binary complex exhibits a strong charge-transfer band at about 1-2eV. Photoexcitation of the ionized system leads to the valence isomerization to the radical cation of octatetraene. The result indicates that ionization of binary complexes enhances the chemical reactivity greatly. With the increase of the concentration of ethylene another product of the composition of C_<10>H_<14> is also found.The present work should be regarded as a pilot study for the future study in the gas phase which is anticipated with the development of short wavelength laser technology.