Abstract

Laser-induced fluorescence (l.i.f.) of the phenyl nitrene (PhN) radical has been observed in the wavelength region 360–370 nm following its production by infrared multiple-photon dissociation of phenyl isocyanate. The transition probes the ground 3A2 state of the species: the upper 3B1 level has a radiative lifetime of 45 ± 3 ns. Ground-state PhN is born vibrationally hot, and collisional relaxation has been studied in the presence of nine added gases, with the efficiencies of the processes depending upon long-range attractive forces between the colliding species. The dissociation process is compared with that of benzylamine, with l.i.f. detection of the 2A2–2B2 transition in the benzyl radical. An upper limit is proposed for the internal energy content of the PhN radical.

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